WO2010114559A1

WO2010114559A1 - Aqueous-based surfactant solution and method of making and using the same

Info

Publication number: WO2010114559A1
Application number: PCT/US2009/039431
Authority: WO
Inventors: David Sabatini; Jeffrey Harwell; Linh Do; Anuradee Witthayapanyanon; Thu Nguyen; Edgar Acosta; Bruce Roberts
Original assignee: The Board Of Regents Of The University Of Oklahoma
Priority date: 2009-04-03
Filing date: 2009-04-03
Publication date: 2010-10-07

Abstract

The present invention relates to an aqueous-based surfactant solution and the method of preparing the surfactant solution. In addition to the surfactant solution itself and the method of preparing the surfactant solution, the present invention describes a method of providing the aqueous-based surfactant solution to extract lipids and oils from biologically derived oil sources. The aqueous surfactant solution includes an aqueous solution and a surfactant to lower the interfacial tension of the lipids and oils to promote the mobility of the lipids and oils from the biologically derived oil sources.

Description

AQUEOUS-BASED SURFACTANT SOLUTION AND METHOD OF MAKING AND USING THE SAME

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0001] A USEPA grant funded a portion of the research for the

present invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] Not Applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

[0003] The present invention relates to an aqueous-based

surfactant solution and the method of preparing the surfactant

solution. In addition to the surfactant solution itself and the method of

preparing the surfactant solution, the present invention describes a

method of providing the aqueous-based surfactant solution to extract

lipids and oils from biologically derived oil sources.

2. Description of the Related Art

[0004] Microemulsions are thermodynamically stable, isotropic

solutions of water and oil that can be stabilized by appropriate

surfactant and/or linker molecules. Microemulsions exhibit many unique properties, such as being transparent and producing ultra low interfacial tension (IFT) and ultra high solubilization. These properties make microemulsions desirable in numerous applications including cosmetics, drug delivery systems, cleaning technologies and soil remediation. Typically, microemulsions created with surfactants have a phase behavior that changes in curvature with surfactant concentration and a tuning parameter, such as electrolyte concentration and temperature. Winsor identified four general types of phase equilibria. As denoted by Winsor, Winsor Type I microemulsions are normal micelles in equilibrium with the excess oil phase, Winsor Type II microemulsions are reverse micelles in equilibrium with the excess water phase and Winsor Type III microemulsions are a bicontinuous phase containing oil, water and surfactant in equilibrium with the excess water and excess oil phase. A Winsor type IV microemulsion occurs when the surfactant concentration is increased in a Type III system, thereby increasing the volume of the middle phase until it becomes a single phase. At low to moderate surfactant concentrations, Winsor Type I, II, and III microemulsions can be produced. The microemulsion transition can be achieved by increasing the electrolyte concentration for ionic and/or increasing temperature for non-ionic surfactants. Increasing electrolyte concentration and/or temperature can cause the surfactant solution to become more hydrophobic and thus segregate more towards the oil-water interface_/ thereby reducing the surfactant film curvature and interfacial tension. At net zero curvature, a Winsor Type III system is formed. [0005] Vegetable oils are lipid materials derived from plants and composed of triglycerides. Often triglyceride oils do not solubilize well into the middle phase microemulsϊon, and a "sponge" phase occurs instead, as demonstrated by several researchers over the past twenty years. Vegetable oils are used not only for cooking purposes but are also receiving broader interest because of the toxicological concerns of using petroleum oils; however, they are considerably more difficult to solubilize in microemulsions. Many attempts have been made at forming vegetable oil microemulsions at ambient condition and without addition of co-oil or alcohols but without success. The reason that vegetable oil microemulsions are elusive appears to be due to the unique structure of triglyceride molecules. Triglycerides are esters of fatty acid with glycerol which contributes to its complicated behavior. The long and bulky alkyl chain lengths make triglycerides highly hydrophobic, while the ester region in the molecule causes high polarity; combined, these lead to poor solubilization. Therefore, conventional surfactants are not able to produce low interfacial tension (<0.1 mN/m) with vegetable oils at ambient conditions without alcohol or co-oil addition. Microemulsion formation with such systems results in liquid crystal, gel formation or sponge phase at ambient conditions [0006] A common method of recovering vegetable oil includes the use of common solvents, such as n-hexane, and pressing. Hexane exposure can cause peripheral nerve damage, thus the extraction of hexane from the vegetable oil microemulsion has to be carefully done. Hexane extraction plants require airtight and leakproof equipment and highly skilled laborers. The EPA and the Clean Air Act have recently set new rules to reduce hexane emissions.

[0007] Accordingly, there remains a need for an aqueous based surfactant solution (environmentally friendly) that does not require a co-oil and/or alcohol to produce a microemulsion of a vegetable oil (or triglyceride) at ambient conditions (temperature and pressure).

SUMMARY OF THE INVENTION

[0008] In one embodiment of the present invention, an aqueous surfactant solution for formulating a product solution from a biologically derived oil source is provided. The product solution includes an oil phase and a water phase. The aqueous surfactant solution includes at least one surfactant having a head and a tail. In addition to the at least one surfactant, the aqueous surfactant solution includes an aqueous solution for contacting with the biologically derived oil source to formulate the product solution. [0009] In another embodiment of the present invention, a method of fabricating an aqueous surfactant solution for formulating a product solution from a biologically derived oil source is provided. The product solution includes an oil phase and a water phase. An aqueous solution and at least one surfactant having a head and a tail are provided. Once the aqueous solution and the at least one surfactant are provided, the aqueous solution and the at least one surfactant are mixed to provide the aqueous surfactant solution. [0010] In a further embodiment of the present invention, a method of forming a product solution from a biologically derived oil source is provided. The product solution includes an oil phase and a water phase. At least one biologically derived oil source is provided. The at least one biologically derived oil source is contacted with an aqueous surfactant solution. The aqueous surfactant solution including at least one surfactant having a head and a tail and an aqueous solution. Once the at least one biologically derived oil source is contacted with the aqueous surfactant solution, a product solution is formed from contacting the aqueous surfactant solution with the at least one biologically derived oil source. The product solution is then collected. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Fig. 1 is a graph view showing dynamic interfacial tension (IFT) versus time.

[0012] Fig. 2 is a graph view showing dynamic IFT versus hydrophilic and lipophilic balance.

[0013] Fig. 3 is a graph view showing the natural log of optimum salinity versus an equivalent alkane carbon number. [0014] Fig. 4 is a graph view showing a microemulsion "fish" diagram in accordance with the present invention. [0015] Fig. 5 i s a graph view showing another microemulsion "fish" diagram in accordance with another embodiment of the present invention.

[0016] Fig. 6 is a graph view showing microemulsion phase behavior in accordance with the present invention. [0017] Fig. 7 is a graph view showing dynamic IFT versus wt% of NaCI in accordance with the present invention.

[0018] Fig. 8 is a graph view showing peanut oil extraction efficiency using different surfactants.

[0019] Fig. 9 is a graph view showing dynamic IFT versus wt% of surfactant in accordance with the present invention. [0020] Fig. 10 is a graph view showing the effect of surfactant concentrations on extraction efficiency in accordance with the present invention.

[0021] Fig. 11 is a graph view showing the effect of shaking speed on oil extraction in accordance with the present invention.

[0022] Fig. 12 is a graph view showing the effect of shaking time on the extractabilϊty of oil in accordance with the present invention.

[0023] Fig. 13 is a graph view showing the effect of salt concentration on the extractability of oil in accordance with the present invention.

[0024] Fig. 14 is a graph view showing the effect of biologically derived oil source-liquid ratio on the extractability of oil in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION [0025] The present invention relates to an aqueous surfactant solution, a method for making the aqueous surfactant solution and a method of using the aqueous surfactant solution to extract lipids from a biologically derived oil source.

[0026] The biologically derived oil source can be any source known in the art that contains lipids (or oils), such as oilseeds, algae, trees and shrubs, such as red cedar, eastern cedar, tea trees, Pongamia pinnata, or the like. An oilseed is a crop or seed containing a vegetable oil. Examples of oilseeds include, but are not limited to, palms, soybean, rapeseed, sunflower seed, peanuts, cottonseed, palm kernel, coconut, olive, corn, hazelnut, other nuts, linseed, rice bran, safflower, sesame, and the like, or a combination thereof. [0027] One embodiment of the present invention is a method of forming a product solution having at least two phases with a low interfacial tension. The at least two phases of the product solution includes an aqueous product phase (also water phase or aqueous phase) and oil phase. The product solution is formed by providing the biologically derived oil source and the aqueous surfactant solution. Once the biologically derived oil source and the aqueous surfactant solution are provided, the biologically derived oil source and the aqueous surfactant solution are contacted to form the product solution. In one embodiment of the present invention, the aqueous surfactant solution and the biologically derived oil source are contacted and ambient temperature and/or ambient pressure. In a further embodiment of the present invention, the aqueous surfactant solution and the biologically derived oil source are contacted to produce the product solution without the use of a co-oil and/or alcohol as a cosolvent. In another embodiment of the present invention, the product solution can include the aqueous product phase, the oil phase, and, optionally, an emulsion phase and/or a biologically derived oil source byproduct. After the product solution is formed, the product solution can be collected. Biologically derived oil source byproducts can include high quality food meal, mulch, or any type of material associated with biologically derived oil source having lipids removed. After collecting the product solution, the oil phase can be separated by any manner known in the art capable of separating the oil phase from the water phase, the emulsion phase, and/or the biologically derived oil source byproduct. Additionally, the biologically derived oil source byproduct can separated from the oil phase, the water phase, and/or the emulsion. Examples of equipment capable of accomplishing the above separations include, but are not limited to, a centrifuge, a decanter, plate and frame pressure filter, rotary vacuum drum filter, pressure leaf filter, and the like. In a further embodiment of the present invention, the water phase and/or the emulsion phase can be recycled to be contacted with the biologically derived oil source. [0028] In a further embodiment of the present invention, the method of forming a product solution having at least two phases can also include the processing of the biologically derived oil source prior to the biologically derived oil source being contacted with the aqueous surfactant solution. Examples of processing can include, but are not limited to, dehulling (for some oilseeds), grinding, running through a separation device (i.e. sieve), cooker, or any combination of these. It should be understood and appreciated that any methods for processing a biologically derived oil source known in the art can be implemented in accordance with the present invention.

[0029] The product solution having at least two phases (oil phase and water phase), created by contacting the biologically derived oil source and the aqueous surfactant solution, has an interfacial tension (IFT) of the at least two phases in a range of less than about 10 mN/m (milli-Newtons/meter). In one embodiment of the present invention, the IFT of the at least two phases is in a range of iess than about 1 mN/m. In yet another embodiment of the present invention, the IFT of the at least two phases is in a range of less than about 0.1 mN/m. In a further embodiment of the present invention, the IFT of the at least two phases of the product solution is in a range of less than about 0.01 mN/m. Additionally, the amount of the oil phase in the product solution increases as the amount of lipids in the biologically derived oil source solubilizing into any emulsion phase in the product solution decreases.

[0030] In accordance with the present invention, the aqueous surfactant solution includes a surfactant for lowering the IFT and thus, increasing the mobilization of lipids in the biologically derived oil source. In another embodiment of the present invention, the aqueous surfactant solution includes a first linker to lower the IFT of the product solution. In a further embodiment of the present invention, the aqueous surfactant solution includes an electrolyte to provide the aqueous surfactant solution with a predetermined salinity. In addition to the first linker, the aqueous surfactant solution can also include a second linker to decrease the equilibration time of the product solution. It should be understood and appreciated that the aqueous surfactant solution can include any combination of the first linker, the second linker, and/or the electrolyte.

[0031] The surfactants are included in the aqueous surfactant solution to increase the mobilization of the lipids from the biologically derived oil source. The surfactants used in accordance with this invention can be any surfactant, typical or extended, capable of increasing the mobilization of the lipids from the biologically derived oil source. Examples of typical surfactants include, but are not limited to, cationic, nonionic, anionic,,amphoteric surfactants, triblock copolymer surfactants, and zwitter-ionic surfactants.

[0032] Generally, surfactants have a head and a tail. An extended surfactant has a head, polar region and a tail, but the transition from the tail to the head is more gradual in an extended surfactant than it is for a typical surfactant. In addition to the more gradual transition from the tail to the head and the polar region, the extended surfactant can extend further into the oil phase of the product solution. Further, the extended surfactants exhibit a considerably lower dynamic interfacial tension (IFT) with lipids (or oils) at ambient temperature and ambient pressure compared to conventional surfactants. Low IFT is crucial to extract lipids and oils from biologically derived oil sources. [0033] Extended surfactants can be any surfactant that has an intermediate polar group (or region) between the head and the tail of the extended surfactant. Examples of extended surfactants include, but are not limited to, linear alkyl-polypropoxylated-sulfates (LAPS) and linear alkyl-polyproxylated-ethoxylated-sulfates (LAPES), branched alkyl-polypropoxylated-sulfate, branched alkyl- polyproxylated-ethoxylated-sulfates, nonionic alkyl-polyproxylated- ethoxylated, nonionic alkyl-polyethoxylated, alkyl-polypropoxylated- carbonate, alkyl-polyproxylated-ethoxylated-carbonate, alkyl- polyproxylated-ethoxylated-sulfonate, and alkyl-poly-ethoxylated- sulfate, and alkyl-polyproxylated-sulfonate.

[0034] Examples of LAPS extended surfactants can be captured by the following formula Ci₆-XPO-SO₄Na, wherein x can be 1 to 20. Examples of LAPES extended surfactants can be captured by the following formula C_y-xPO-zEO-SO₄Na, wherein y can be 1 to 22, x can be 10, 12, 14, and 18, and z can be 1 to 20. It should be understood and appreciated that the extended surfactant can be any one of these extended surfactants or a combination thereof.

[0035] The surfactant can be provided in the aqueous surfactant solution in any amount such that the aqueous surfactant solution and the biologically derived oil source, when contacted with one another, produce the product solution having at least two phases. In one embodiment of the present invention the extended surfactant is present in the aqueous surfactant solution in an amount in a range of from about 0.01 wt% to about 5.0 wt% of the aqueous surfactant solution. In another embodiment of the present invention the extended surfactant is present in the aqueous surfactant solution in an amount in a range of from about 0.1 wt% to about 1.0 wt% of the aqueous surfactant solution.

[0036] Linkers (or linking agents) are amphiphiles that segregate near a membrane of a microemulsion. Generally, a lipophilic linker will partition near the tail of a surfactant whereas a hydrophilic linker will segregate near the head of a surfactant. Linkers can be used to improve the interaction of the membrane in either the water phase or oil phase of the product solution. It should be understood and appreciated that while lipophilic and hydrophilic linkers are discussed herein, any type of linker known in the art that can be used with the surfactant to produce the product solution in accordance with the present invention can be used.

[0037] In one embodiment of the present invention, the first linker is a lipophilic linker that partitions near the tail of the extended surfactant to improve interaction of the extended surfactant with the water phase of the product solution. Addit ionally, lipophilic linkers disrupt the formation of any liquid crystal phase at the interface of the water phase and the oil phase of the product solution. Examples of lipophilic linkers include, but are not limited to, long chain alcohols, such as oleyl alcohol, dodecanol, decanol, any alcohol with greater than 8 carbons is considered a lipophilic linker, also glycerol monoleate, sophorolϊpids, and surfactants with a hydrophilic-lipophillic balance (HLB) less than 5. It should be understood and appreciated that any lipophilic linker can be used such that the product solution can be produced in accordance with the present invention. It should also be understood and appreciated that while one example of a lipophilic linker is an alcohol it is not provided in an amount sufficient to make it a cosolvent, nor does it perform the same function as that of an alcohol cosolvent.

[0038] The first linker can be present in the aqueous surfactant solution in any amount such that the aqueous surfactant solution and the biologically derived oil source, when contacted with one another, produce the product solution. In one embodiment of the present invention the first linker is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt% to about 5.0 wt% of the aqueous surfactant solution.

[0039] In another embodiment of the present invention, the second linker is a hydrophilic linker that partitions near the head of the extended surfactant to improve interaction of the extended surfactant with the oil phase of the product solution. Like the lipophilic linker, the hydrophilic linker disrupts the formation of any liquid crystal phase at the interface of the water phase and the oil phase of the product solution. Examples of hydrophilic linkers include, but are not limited to, polyglucoside, xylene sulfonate, sodium mono- and dimethyl naphthalene sulfonate (SMDNS), and surfactants with an HLB greater than 12. It should be understood and appreciated that any hydrophilic linker can be used such that the product solution can be produced in accordance with the present invention.

[0040] The second linker can be present in the aqueous surfactant solution in any amount such that the aqueous surfactant solution and the biologically derived oil source, when contacted with one another, produce the product solution. In one embodiment of the present invention the second linker is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt% to about 5.0 wt% of the aqueous surfactant solution.

[0041] In a further embodiment of the present invention, the first linker and the second linker can be interchanged. Thus, the first linker would be a hydrophilic linker and the second linker would be a lipophilic linker. It should be understood and appreciated that the same lipophilic and hydrophilic linkers described herein could still be used.

[0042] The electrolyte (or salt) is added to the aqueous surfactant solution to provide the aqueous surfactant solution with a predetermined (or optimum) salinity. The electrolyte is also added to promote better packing of the surfactants around the lipids thus increasing the mobility of the lipids from the biologically derived oil source. Examples of electrolytes include, but are not limited to, NaCI, CaCb or any salt that increases the ionic strength of the solution without precipating the surfactant(s) used in the solution. It should be understood and appreciated that any electrolyte can be used such that the requisite salinity can be attained and the product solution can be produced in accordance with the present invention. [0043] The electrolyte can be present in the aqueous surfactant solution in any amount such that the aqueous surfactant solution and the biologically derived oil source, when contacted with one another, produce the product solution. In one embodiment of the present invention the electrolyte is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt% to about 10 wt% of the aqueous surfactant solution.

[0044] Another embodiment of the present invention is a method of fabricating the aqueous surfactant solution. This method includes providing the surfactant and providing an aqueous solution. Once the surfactant and the aqueous solution are provided, the surfactant and the aqueous solution are mixed to provide the aqueous surfactant solution. In another embodiment of the present invention, the first linker is provided to lower the IFT of the product solution. In addition to the inclusion of the surfactant and the first linker, the aqueous surfactant solution can be provided with the electrolyte to provide the aqueous surfactant solution with a predetermined salinity. In a further embodiment of the present invention, the second linker is included in the aqueous surfactant solution to decrease the equilibration time of the product solution. It should be understood that the extended surfactant, first linker, electrolyte, and second linker discussed in accordance with this embodiment are the same as those discussed herein.

EXPERIMENTAL PROCEDURES Materials [0045] Two classes of anionic extended-surfactants were studied in this work, including linear alkyl-propoxylated-ethoxylated-sulfate (LAPES) surfactants and linear alkyl-propoxylated-sulfate (LAPS) surfactants. The number of EO and/or PO groups were varied among each class of surfactant. The extended -surfactants were kindly provided by Huntsmann Chemical Co. (Houston, TX) and used as received. The extended-surfactants studied and their properties are summarized in Table 1. The hydrophilic-lϊpophilic balance (HLB)of the surfactants were estimated using Equation (1):

HLB = 7 + (#EO) + (#PO) + (#CH₃) + Sulfate (1)

Table 1: Properties of extended-surfactants

^♦Estimated from Equation(l)

[0046] Triolein 65% practical grade, peanut, soybean and olive oils were purchased from Sigma Chemical Co. (St Louis, MO). Canola, corn and sunflower oils were purchased from the local market. Typical triglyceride compositions of several of these oils are summarized in Table 2. Sodium chloride +99% purity was purchased from Fluka Chemical Corp. (Milwaukee, WI). Polyglucoside (Glucopon IM425 50 active%) was kindly provided by Cognis - Care Chemicals, sodium mono- and dimethyl naphthalene sulfonate (SMDNS) was received from CKWitco (Houston, TX). Oleyl-alchohol or fatty alcohol at 85% active was purchased from Aldrich (St Louis, MO). Pentane, hexane, n-heptane, n-decane, n-dodecane, n-hexadecane (+99% purity) were purchased from Sigma-Aldrich (St Louis, MO). Table 2: Main fatty acid compositions (%) of some oils:

Oil/Component C16:0 C18:0 C18:l C18:2 C18:3

(P-Palmitic) (S-Stearic) (O-Oleic) (L-Linoleic) (Ln-Linolenic)

Triolein 3.66 N/A 65 N/A 7.36

(65% practical grade)*

Peanut** 13 3 41 38 N/A

Olive** 10 2 78 7 1

Canola** 4 2 56 26 10

*Data from manufacturer

**Data from Salager J. L, Bourrel R.S., and Wade W. H. "Mixing rules for optimum phase behavior formulations of surfactant/water/oil systems. Soc. Petrol. Eng. J,, 19, 271-78 (1979).

Methods

[0047] Dynamic interfacial tension experiments were performed to evaluate the interaction of extended-surfactant systems with triolein and vegetable oils. These experiments were carried out using a spinning drop tensiometer purchased from the University of Texas (Model 500). All surfactant solutions were 0.1 wt% for salinity scans. Each sample run was conducted in triplicate and recorded every five minutes for a twenty minute time frame.

[0048] Phase behavior experiments were carried out by scanning a single parameter of the formulation (for example, by varying salinity, surfactant concentration, etc). Five ml_s of surfactant solution and five ml_s of oil were added into a 15 ml_ glass vial tube. The solutions were gently shaken three times a day for three days and left for two weeks to ensure equilibrium. At a constant surfactant and linker concentration, the optimum formulation is obtained at the optimum salinity concentration, as denoted by S* (expressed in wt%). Recalling from the Winsor R ratio definition, the optimum formulation is obtained when R = 1, or surfactant interactions on both the water side and the oil side are equal to each other.

Oil Content

[0049] To provide a baseline of extracted oil, crude peanut and canola oils were extracted with hexane by Soxhlet extraction method following the Association of Analytical Communities (AOAC) standard procedure. The amount of oil extracted was evaluated as the total oils present in peanut/canola seeds. In this method, the Soxhlet extractor was heated to 60⁰C on a mantle. The thimble was filled with 5 grams of peanut/canola seeds and extracted for 4 hours. Hexane containing extracted peanut and canola oils were evaporated in the hot air oven at 7O⁰C until no change in mass of the oils were observed to eliminate residua] hexane. Total oil analysis gave 42% peanut and 40% canola oil based on dry weight basis. These values are in the range reported in the literature. Oil extraction efficiency was calculated as percentage of oil extracted divided by the total oil present in the seeds as determined by this method.

Oil Extraction

[0050] One example of an aqueous extended-surfactant based method of extraction of peanut oil and canola are summarized in hereafter. Peanut seeds were dehulled, whereas canola seeds were not since it is not economically feasible to dehull canola seeds. The oilseeds were then oven-dried at 104⁰C for 35 minutes to inactivate myrosinase enzymes, gossypols and other unfavorable compounds. After being fully pretreated, oilseeds were put into the micellar and electrolyte solution in a 25 ml_ glass tube. Then, the tubes were put in the shaker in horizontal configuration. The solution was subsequently centrifuged at 6000 rpm to separate the oil into three different parts: oil free phase, protein rich meal and aqueous surfactant recovery phase. The meal was dried in an oven at 104⁰C overnight for oil residual analysis by Soxhlet extraction method, allowing a complete mass balance to be conducted. Triglyceride Composition Profile

[0051] The triglyceride composition (TGC) profile was obtained by reversed-phase high-performance liquid chromatography (RP-HPLC) with an evaporative light scattering detector (ELSD). The mobile phases were dϊchloromethane and acetonitrile. The column used was Alltima HP C18 Hi-Load, 3mm, 150 x 3 mm. TGC peaks were indentified based on the retention time of standards and the results in Alltech application book. Peak areas were used to quantify the components based on relative percentages.

Oil Quality Analysis

[0052] Free fatty acid content was determined according to AOAC standard procedures. The oil stability was tested by a 12 hour cold test at O⁰C method.

RESULTS

Ultralow interfacial tension values (IFTs) with triglyceride oils: [0053] Rg. 1 shows dynamic IFT values of Aerosol-OT(AOT), which is a conventional surfactant, and Ci2-14PO-2EO at optimum salinity (S*) with canola oil, and Ci₂-14PO-2EO at S* with triolein, corn, and peanut oils. The optimum salinity (S*) produces the minimum IFT for a given surfactant system. From Fig. 1, it can be seen that Ci₂-14PO-2EOsulfate produced IFT values two to three orders of magnitude lower than AOT within 10-15 minutes. It is important to note that these results were obtained at ambient condition and with no addition of co-oil or cosolvent alcohol. These ultralow IFT values have not been reported for these vegetable oils at ambient conditions without the addition of an alcohol or co-oil. The extended-surfactant was able to reach equilibrium within a fifteen minute time frame. This result is very important for industrial application as IFT reduction occurs in a reasonable time frame for system scale up.

[0054] Fig. 2 shows triolein dynamic IFT values using the two classes of extended -surfactants listed in Table 1 (LAPS and LAPES). As can be seen from Fig. 2 , all three extended-surfactants produced ultralow IFT values (<0.1 mN/m); recall that the conventional surfactant AOT was unable to do so (> 1 mN/m as seen in Fig. 1). The LAPES surfactants produced IFT values as low as 10^"3 mN/m. Comparing the two classes of surfactants, both LAPES surfactants (ClO and C12) show lower IFT values than LAPS surfactants. It is important to note that, although ultra low IFT values were observed, middle phase microemulsion systems (or Winsor Type III) were not formed using extended-surfactants alone with triolein and vegetable oils; rather, sponge phases or white milky phases were observed. For comparison purposes, select studies were conducted with hexadecane. Extended-surfactants were able to form a middle phase microemulsion (Winsor Type III) with hexadecane (EACN = 16) (data not shown), while extended -surfactants were unable to form a middle phase microemulsion with vegetable oils with similar EACN values (EACN 16- 19). Winsor Type I and Type II microemulsions were formed with triolein and vegetable oils with white milky excess oil or water phases, respectively, with negligible solubilization at even high surfactant concentration (i.e. 8wt%). Even at higher temperature, such as 35⁰C, no middle phase microemulsion was observed. The failure to form middle phase microemulsions using extended -surfactant alone in this work is likely due to the poor interactions of the surfactant molecule with the triglyceride oil. Poor solubilization is desirable in certain applications such as vegetable oil extraction, where high solubilization would require difficult oil-surfactant separation and surfactant recovery processes.

Determination of equivalent aikane carbon number of vegetable oils: [0055] The equivalent aikane carbon number (EACN), which represents the oil's hydrophobϊcity, is an important parameter in producing an optimal formulation. EACN values of the oils can be found by using the semi-empirical equation proposed by Salager et al. : In(S*) = k(EACN) + (A) - σ + <χ_τΔT (2)

[0056] where S* is the optimum electrolyte concentration; k is a constant reflective of the head group, normally between 0.1 to 0.17; EACN is the equivalent alkane carbon number for unsaturated hydrocarbons (for saturated alkanes, by definition the value equals the number of carbons); σ is a function of the surfactant type; α is a constant; f(A) is a function of alcohol; and ΔT is the temperature difference between the studied temperature and a reference temperature. Since in our study, we did not use alcohol and we kept the temperature constant, Equation (2) can be simplified to:

In(S*) = k(EACN) - σ (3)

[0057] Experimental procedures for determining the EACN values for oils has been described in Acosta et al. where they determined the EACN values of isopropyl myristate and squalene. In our research, we conducted a sodium chloride scan at a fixed 0.1 wt% Ci₂-12PO-2EO- sulfate surfactant concentration for different oils. The IFT values were recorded after equilibrium was reached, i.e. until no change in IFT value was observed. Alkane oils with known EACN values, including pentane (5), hexane (6), n-heptane (7), n-decane (10), n-dodecane (12) and n-hexadecane (16), were used as reference oils. The natural logarithm of S* values were plotted against EACN values of the reference oils to establish the correlation; from Equation (3), the correlation should produce a linear relationship. EACN values of triolein and vegetable oils can be easily found by measuring their S* and establishing their EACN values using the correlation curve established for oils with known EACN values.

[0058] Fig. 3 shows the resulting InS* versus EACN values of reference oils and interpreted EACN values of triolein (65% practical grade) and vegetable oils on the same plot. A good correlation was obtained for the fit to the alkane data (R² value at 0.99). Using Ci₂- 12PO-2EO extended -surfactant, the fitting equation for reference oils is:

InS* = 0.104(EACN) + 0.031 (4)

[0059] The K value of 0.104 is within the reasonable range as mentioned above (0.1 to 0.17). From Equation (4) the surfactant constant (σ) for Ci₂-12PO-2EO extended-surfactant was found to be at -0.031. Based on their S* with Ci₂-12PO-2EO surfactant and using the correlation in Fig. 3 and Equation (4), the EACN values of triolein 65% practical grade and vegetable oils are shown in Table 4. [0060] As can be seen from Table 4, vegetable oils studied in this work are generally very hydrophobic with EACN values ranging from 17 to 19. Surprisingly, the triolein (65%) shows a negative EACN value of -0.3. From Table 2, we observe that triolein (C18: l) is the major triglyceride in the other oils studied, and we thus expected triolein to have a similar EACN to these other oils. However, since we did not use pure triolein, we suspect that impurities in the studied triolein (such as free fatty acid compositions) might contribute to its hydrophilicity.

Microemulsification of Triolein 65% practical grade [0061] Since the studied triolein (65% practical grade) has a very low EACN, a hydrophilϊc linker was used to improve interaction of the surfactant system with the water side of the interface. A hydrophilic linker, sodium mono- and dimethyl naphthalene sulfonate (SMDNS), scan and salinity scan were performed by fixing the surfactant concentration at 3 wt%; this higher surfactant concentration made it easier to visually observe middle phase formation. The optimum surfactant for a given oil should have the lowest salt and hydrophilic linker concentration. When adding the hydrophilic linker up to 1.2 wt%, a normal microemulsion transition behavior from Wϊnsor Type I- III-II was observed. At lower linker concentrations, a microemulsion phase was not observed; instead, a white and milky phase was observed. Fig. 4 represents the microemulsion phase diagram of triolein using Ci₀-18PO-2EO, SMDNS as a hydrophilic linker at ratio (3/1.2), and sodium chloride. In addition, all the LAPES extended- surfactants studied in this work were able to form middle phase microemulsions at the ratio of surfactant to linker of 3: 1.2 by weight (data not shown). Among LAPES extended-surfactants, the lowest triolein S* value was observed with Cio-18PO-2EO surfactant. The "fish" diagram in Fig. 4 slants to the right with increasing total surfactant and linker concentrations, suggesting a stronger interaction with the water at higher concentration and thus a higher S* required to balance the surfactant at the interface.

Microemulsification of vegetable oils

[0062] As discussed above, vegetable oils are mixture of triglycerides, free fatty acids and other components, with triglycerides making up the greatest fraction. Since triglycerides are esters of fatty acids and a triglycol, many combinations are possible (i.e 000, LnLnO and POO; see Table 3 for abbreviations) resulting in a mixture of very complicated and different fraction of individual triglycerides. An ideal surfactant formulation would be one that can form microemulsions with a range of vegetable oils regardless of the different fraction of triglycerides in vegetable oils. As expected, when applying the Cio- 18PO-2EO/SMDNS system that formed a middle phase with the low EACN triolein (-0.2) to the vegetable oils with much higher EACN values, no microemulsion phase was formed with the vegetable oils. The EACN values of vegetable oils range from 16 - 19 (see Table 4) and are much higher than the triolein studied here; therefore, the formulation optimized for triolein is not compatible with vegetable oils. In addition, when mixing this formulation with vegetable oils, a milky viscous white phase was formed in the oil phase which indicates weak interactions and poor solubilization in the oil phase. Table 3: Some common triglycerides in vegetable oils and their abbreviations:

Table 4: Measured EACN values of oils

[0063] To balance the system for the higher EACN vegetable oils, a long chain alcohol was added as a lipophilic linker. In this study, we used oley! alcohol as the lipophilic linker. A phase study of vegetable oils with extended-surfactants and lipophilic linker was performed, using procedures similar to that used with the hydrophilic linker mentioned above. The phase study using surfactant and lipophilic linker alone showed no microemulsion formation. Instead, white, milky and multiple-phases were observed at any sodium chloride concentration. This is likely due to the fact that the surfactant film at the water-vegetable oil interface had difficulty in penetrating the large triglyceride molecules. This possibly suggests that both lipophilic and hydrophilic linkers may be used to overcome the poor solubilization. Systems of Ci₀-18PO-2EO and SMDNS at ratio 3/1.2 was fixed at 4.2wt% total concentration and oleyl alcohol and sodium chloride were scanned for peanut oil. A normal microemulsion Wϊnsor Type I-III-II transition was observed when oley! alcohol (lipophilic linker) concentration reached 2.5wt% (data not shown). However, the sodium chloride concentration to obtain middle phase microemulsion for this system was very high at 15wt%, which would be infeasible in many applications.

[0064] In order to reduce the salinity level, a hydrophilic linker which is more hydrophobic than SMDNS was selected. Glucopon, which is a mixture of polyglucosides, was used as a replacement for SMDNS. By using glucopon, S* reduced from 15wt% to 7.5wt% at 6.7wt% total surfactant and linker concentration. Fig. 5 illustrates the "fish" diagrams of olive oil, peanut oil and canola oils with this surfactant system. Similar results were observed with other vegetable oils including corn, sunflower, sobyean and cottonseed oils (data not shown). At high total surfactant and linker concentration (more than 3 wt%) the formulation reached equilibrium within four hours. At lower concentration (less than 1 wt%), the system required two weeks to reach equilibrium. A Winsor type IV microemulsion was also observed with all studied vegetable oils at total surfactant and linker concentrations at 16.7 wt% at low sodium concentration (4 - 5 wt%) and with the solubilization parameters ranging from 6 - 10 ml/mg. The microemulsion with canola oil exhibits the lowest solubilization parameter at 6 ml/mg, while peanut oil showed the highest solubilization capacity at 10 ml/mg. From the fatty acid compositions in Table 2, canola oil has the highest fraction of the unsaturated fatty acid, up to 92%, whereas peanut oil has the lowest of 86%. Higher fraction of triglyceride in the oils might contribute to the lower solubilization capacity. This also might be the explanation for the larger fish "body" of peanut oil microemulsion. These results appear to be the first report of Winsor Type I - IV microemulsion formation with vegetable oils at ambient conditions and without the addition of co-oils and/or alcohols. [0065] Fig. 6 shows the fish diagram with peanut oil, using the same linker systems at the same ratio, but using two classes of extended-surfactants, Ci₀-18PO-2EO (LAPES) (as in Fig. 5) and Ci₆- 10.7PO (LAPS). In Fig. 6, the fish "body" of Ci₀-18PO-2EOsulfate system slants to the left with increasing total surfactant and linker concentrations. In contrast, the fish body of C_i6-10.7POsulfate slants to the right with increasing total concentrations. Recalling from Fig. 2, the LAPS extended -surfactant shows higher IFT values than LAPES surfactants. Formulation using C_i6-10.7POsulfate (LAPS) shows much poorer solubilization capacity (4ml/mg) than Cio-18PO-2EOsulfate (LAPES) (10ml/mg) with peanut oil. This is interesting given the longer alkyl chain of the Ci₆-IO.7POsulfate, and suggests that the 18PO- 2EOsulfate combination more than offsets the shorter ClO alkyl group of the LAPES surfactant.

[0066] HLB values of Ci₀-18PO-2EOsulfate and Ci₆-10.7POsulfate are 38.5 and 36.5, respectively (see Table 1). Such small HLB difference might not account for the difference in the phase behavior. Rather, the difference might be due to the behavior of the extended- surfactants at the oil - water interface in a way that is not understood. It can be concluded that for different applications, various extended- surfactants can be used. For formulation that is required to form a Winsor Type IV microemulsion, like many cleaning products, a Cio- 18PO-2EOsulfate system could be used since it exhibits low S* at high concentration, and vice versa.

Salinity Concentration

[0067] It is well-known that the salt content in the surfactant solution can be tuned to lower the interfacial tension. The amount of sodium chloride in the surfactant solution greatly impacts the phase behavior of the mixture, which in turn alters the interfacial tension and ultimately affects vegetable oil recovery. In order to find the optimum salinity concentration for edible oil extraction, IFT experiments of vegetable oils, namely canola, peanut oil with Cio-18PO-2EOSθ₄l\la were performed. The optimum salt concentration for peanut oil was found to be at 6wt% and for canola oil was at 5wt% as shown in Fig. 7. Additional factors affecting vegetable oil extraction efficiency are discussed below.

Effect of surfactant types

[0068] Fig. 8 shows a comparison of extraction efficiencies of surfactant systems for vegetable oil extraction. All surfactant concentrations were prepared at 0.15wt% and at optimum salt concentrations. The surfactants studied are C16-10.7POsulfate, C12- 14PO-2EOsulfate, and Ci₀-18PO-2EOsulfate. As a baseline, Fig. 8 also shows the extraction efficiency using water as the extraction solution. It can be seen that water exhibits the lowest extraction efficiency which is about 40%. Ci₅-IO.7P0sulfate gives a somewhat higher efficiency of 65%. However, both water and Ci₆-10.7POsulfate produce stable emulsion-like phases which are not desirable in the extraction process. Ci₂-14PO-2EOsulfate and Ci₀-18PO-2EOsulfate both give very high peanut oil extraction efficiencies of 92-95%. However, only the Cio-18PO-2EOsulfate produced a neat oil free phase, whereas Ci₂- 14PO-2EOsulphate produced an undesirable emulsion-like phase.

Effect of surfactant concentrations

[0069] As mentioned previously, the mobilization mechanism is desirable in edible oil extraction and it can be achieved at low surfactant concentration (i.e. less than 0.5wt %) when ultra low IFT values are achieved. The lowest surfactant concentration producing this ultra low IFT value is the critical microemulsion concentration (CμC) To explain the concept of the CμC, it is helpful to first discuss the critical micelle concentration (CMC), which is the minimum surfactant concentration required to form micelles. Above the CMC, surfactant molecules form aggregates called micelles in which surfactant molecules are arranged in a spherical pattern, with the hydrophobic tails oriented inward (towards the center of the sphere) and the hydrophϊlic tails oriented outward toward the water phase. In this micellar configuration the surfactant aids in lowering the interfacϊal tension between the water phase and the oil phase, thus allowing for the improvement of oil extraction. The CμC is above the CMC. [0070] Fig. 9 shows the IFT values versus surfactant concentrations for surfactant and peanut oil and canola oil, respectively. From this, it was found that the CμC value of C₁₀-I8PO- 2E0sulfate with peanut oil is 0.2 wt% and that with canola oil is 0.35wt%. The surfactant concentrations were varied above and below the CμC values for peanut oil and canola oil to study the effect of surfactant concentrations on oilseed after extraction as illustrated in Fig. 10. The two figures show very good agreement between the trends of the extraction efficiency and the CμC values reported above. As surfactant concentrations increase to the CμC points, dramatic increase in both canola and peanut oil extraction efficiencies are observed. At the surfactant concentrations higher than the CμC, the oil extraction efficiency plateaus. Thus, optimum formulation for peanut oil extraction is 0.2 wt% of Cio-18PO-2EOsulphte and 6wt% NaCI, and optimum formulation of canola oil extraction is 0.35 wt% of C₁0-I8PO- 2E0sulphate and 5wt% NaCI.

Effect ofpH on extraction efficiency

[0071] Four different pH values were studied, including pH of 4, 7, 9 and 11 (data not shown) with peanut and canola oil extraction. In contrast to aqueous extraction methods using enzymes, pHs ranging from 4 to 9 do not have much effect on the extraction efficiency, which is consistent with the IFT results (data now shown). At pH 11, the solution suddenly changes into green-brownish color and the extraction drops sharply since green-brownish emulsion was observed instead of a clear oil phase. This can be explained by the solubilization of protein in the aqueous phase at pH 11.

Effect of shaking speed

[0072] The impact of mixing intensity (shaking speed) was evaluated in this experiment, the mass of the oilseed, surfactant concentration and salt concentration were fixed at 2 grams, 0.1 wt% and 6 wt%, respectively. Different agitation speeds of 50, 100, 150, 200, 250 and 300 shakes/min were studied and the results reported in Fig. 11. It can be seen from the graph that the low agitation speed (50 shakes/min) has lower oil extraction efficiency. However, at shaking speeds higher than 150 shakes/min, the shaking speed no longer has a significant effect on vegetable oil extraction. It was observed that at the highest shaking speed of 300 shakes/min, stable fine solid was formed and settled slowly which leads to the problem in the separation of the fine solid from the oil phase. Based on these results, the shaking speed at 100-150 shakes/min was used in subsequent experiment. Effect of shaking time

[0073] From the dynamic IFT results shown in Fig. 9, the equilibrium IFTs of surfactant solutions with peanut oil and canola oil were obtained within 20 minutes. Therefore, it is expected that the amount of oil extracted will not change after 15 minutes at 100 shakes/min. This is in good agreement with results in Fig. 12, which shows that the extraction efficiency plateaus at 20-25 minutes. Besides, the dynamic IFT of the used surfactant solution still exhibits ultralow interfacial tension with the vegetable oil; therefore we expect this solution can be easily recycled.

Effect of salinity concentrations

[0074] Salinity scans were performed at a fixed surfactant concentration of 0.1 wt%, as seen Fig. 10. Dynamic IFT results suggested that the optimum salt concentration for peanut oil at 6 wt%, (Fig. 10), this is in excellent agreement with the oilseed extraction experiments in Fig. 13, respectively. However, at 5 wt% and 8 wt% of NaCI concentrations, it is observed that while the dynamic IFT results are relatively similar, the amount of oil extracted varies.

Effect of solid-liquid ratio on extraction efficiency [0075] Different solid-liquid ratios of 2 to 5, 2 to 8, 2 to 10, and 2 to 15, as shown in Fig. 14, were investigated. It can be seen that at low or high solid to liquid ratio, the extraction efficiency decreases. The optimum extraction efficiency was obtained at 2 : 10 for peanut oil in Fig. 14. The same result was observed with canola oil (data not shown). The amount of oil extracted decreased at the highest solid - liquid ratios since the viscosity of mixture increases made it difficult to maintain mixture homogeneity and to achieve surfactant-oilseed contact. Conversely, we speculate that at too using too high liquid to solid ratio causes less particle collision, leading to poor extraction efficiency. It is important to note that compared to other aqueous extraction processes studied in the literature, we are able to achieve a higher solid-liquid ratio. A ratio of 1:20 is normally observed in other studies.

Oil quality

[0076] The crude oil quality resulting from the aqueous extended- surfactant based method was analyzed and compared to the hexane method. Parameters that were compared include free fatty acid concentration, triglyceride composition profile and the oil clarity. The analytical results are summarized in Table 5 and 6 for peanut oil and canola oil, respectively. It can be seen that the oil quality obtained by aqueous extended-surfactant is comparable with those for commercial sample and hexane extracted oil. The hexane-extracted oil has significantly higher content of free fatty acid. The triglyceride composition profiles for peanut and canola oils obtained by our method are also illustrated in Table 5 and 6, respectively. Vegetable oils are mixture of triglycerides, free fatty acids and other components, with triglycerides making up the greatest fraction. Since triglycerides are esters of fatty acids and a triglycol, many combinations are possible (e.g. 000, LnLnO and POO; see Table 5 for abbreviations) reustling in a mixture of complicated and different fractions of individual triglycerides. The interpretation of the triglyceride composition profile from retention data was based on the method described in Peter et al. paper. The aqueous extended-surfactant-based method produced vegetable oil with triglyceride profiles similar to those obtained from hexane method and the commercial vegetable oil products.

Table 5: Analysis of peanut oil

Abbreviations:

Ln: C18:3

L: C18:2

O: C18:1

S: C18:0

P: C16:0

%FFA: percentage of free fatty acids

[0077] From surfactant selections studies, it has been shown that, among different classes of extended-surfactants studied, the linear alkyl-propoxylated-ethoxylated-sulfate class of surfactants is most suitable for the vegetable oilseeds evaluated in this research since it produces the lowest interfacial tension (IFT). Additionally, the Ci₀- 18PO-2EO-sulfate exhibits the best performance for vegetable oil extraction in terms of low IFT, salinity values and absence of stable macroemulsions. The aqueous extended-surfactant based method has been proved to be effective for extracting peanut and canola oils, being able to achieve 95% and 93% oil extraction, respectively. Although the extraction efficiency is not as high as that of the hexane method, which has 98-99% efficiency, this method offers significantly better crude oil quality in terms of free fatty acid and phospholipids content.

[0078] The effects of different processing parameters on vegetable oil extraction efficiency, including pH, surfactant concentration, extraction time, shaking speed, solid-to-liquid ratio, and salinity levels were also looked at. It was found that surfactant concentrations at the CμC and optimum salt concentrations are the most efficient for vegetable oil extraction efficiency. The quality of vegetable oil extracted by using aqueous extended-surfactant-based method as compared to the hexane extraction method were also evaluated. From the evaluation of crude oil quality, it was shown that this method offers better crude oil quality in terms of free fatty acid content compared to the hexane extraction method. The triglyceride profile of surfactant-extracted oil is very similar to that of the market oil. The peanut and canola oils are clear and exhibit pleasant smell. Thus, it has been successfully demonstrated the viability of the aqueous surfactant based extraction method for seed extraction of vegetable oils. [0079] From the above description, it is clear that the present invention is well adapted to carry out the objectives and to attain the advantages mentioned herein as well as those inherent in the invention. While presently preferred embodiments of the invention have been described for purposes of this disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art and which are accomplished within the spirit of the invention disclosed and claimed.

Claims

What is claimed is:

1. An aqueous surfactant solution for formulating a product solution from a biologically derived oil source, the product solution having an oil phase and a water phase, comprising: at least one surfactant having a head and a tail; and an aqueous solution for contacting with the biologically derived oil source to formulate the product solution.

2. The solution of claim 1 further comprising: a first linker to for lowering interfacial tension of the product solution created by contacting the biologically derived oil source and the aqueous surfactant solution; and an electrolyte to give the aqueous surfactant solution a predetermined salinity.

3. The solution of claim 1 further comprising a second linker to decrease the equilibration time of the product solution created by contacting the biologically derived oil source and the aqueous surfactant solution.

4. The solution of claim 2 wherein the first linker is a lipophilic linker that partitions near the tail of the surfactant to improve interaction of the surfactan t with the water phase of the product solution.

5. The solution of claim 3 wherein the second linker is a hydrophilic linker that partitions near the head of the surfactant to improve interaction of the surfactant with the oil phase of the product solution.

6. The solution of claim 4 wherein the first linker is selected from the group consisting of a long chain alcohol, dodecanol, decanol, any alcohol with greater than 8 carbons, glycerol monoleate, sophorolipids, surfactants with a hydrophilic-lipophillic balance (HLB) less than 5, and combinations thereof.

7. The solution of claim 5 wherein the second linker is selected from the group consisting of polyglucoside, sodium mono- and dimethyl naphthalene sulfonate, xylene sulfonate, surfactants with a HLB greater than 12, and combinations thereof.

8. The solution of claim 1 wherein the at least one surfactant is a conventional surfactant selected from the group consisting of anionic, cationic, nonionic, amphoteric, zwitter ionic, triblock copolymers, and combinations thereof.

9. The solution of claim 1 wherein the at least one surfactant is an extended surfactant selected from the group consisting of a linear alkyl-polypropoxylated-sulfate, a linear alkyl-polypropoxylated- ethoxylated-sulfate, and combinations thereof.

10. The solution of claim 9 wherein the at least one extended surfactant is present in the aqueous surfactant solution in an amount in a range of from about 0.01 wt % to about 5.0 wt %.

11. The solution of claim 9 wherein the at least one extended surfactant is present in the aqueous surfactant solution in an amount in a range of from about 0.1 wt % to about 1.0 wt %.

12. The solution of claim 4 wherein the first linker is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt % to about 5.0 wt %.

13. The solution of claim 5 wherein the second linker is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt % to about 5.0 wt %.

14. The solution of claim 2 wherein the electrolyte is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt% to about 10.0 wt%.

15. The solution of claim 2 wherein the electrolyte is selected from the group consisting of NaCI₇ CaCb, and a combination thereof.

16. A method of fabricating an aqueous surfactant solution for formulating a product solution from a biologically derived oil source, the product solution having an oil phase and a water phase, comprising the steps of: providing an aqueous solution; providing at least one surfactant having a head and a tail; and mixing the aqueous solution and the at least one surfactant to provide the aqueous surfactant solution.

17. The method of claim 16 further comprising the steps of: providing a first linker for lowering interfacial tension of the product solution created by contacting the biologically derived oil source and the aqueous surfactant solution; and providing an electrolyte to give the aqueous surfactant solution a predetermined salinity.

18. The method of claim 16 further comprising the step of providing a second linker to decrease the equilibration time of the product solution created by contacting the biologically derived oil source and the aqueous surfactant solution.

19. The method of claim 17 wherein the first linker is a lipophilic linker that partitions near the tail of the surfactant to improve interaction of the surfactant with the water phase of the product solution.

20. The method of claim 18 wherein the second linker is a hydrophilic linker that partitions near the head of the surfactant to improve interaction of the surfactant with the oil phase of the product solution.

21. The method of claim 19 wherein the first linker is selected from the group consisting of a long chain alcohol, dodecanol, decanol, any alcohol with greater than 8 carbons, glycerol monoleate, sophorolipϊds, surfactants with a hydrophilic-lipophillic balance (HLB) less than 5, and combinations thereof.

22. The method of claim 20 wherein the second linker is selected from the group consisting of polyglucoside, sodium mono- and dimethyl naphthalene sulfonate, xylene sulfonate, surfactants with a HLB greater than 12, and combinations thereof.

23. The method of claim 16 wherein the at least one surfactant is a conventional surfactant selected from the group consisting of anionic, cationic, nonionic, amphoteric, zwitter ionic, trϊblock copolymers, and combinations thereof.

24. The method of claim 16 wherein the at least one surfactant is an extended surfactant selected from the group consisting of a linear alkyl-polypropoxylated-sulfate, a linear alkyl-polypropoxylated- ethoxylated-sulfate, and combinations thereof.

25. The method of claim 24 wherein the at least one extended surfactant is present in the aqueous surfactant solution in an amount in a range of from about 0.01 wt % to about 5.0 wt %.

26. The method of claim 24 wherein the at least one extended surfactant is present in the aqueous surfactant solution in an amount in a range of from about 0.01 wt % to about 5.0 wt %.

27. The method of claim 19 wherein the first linker is present in the aqueous surfactant solution in an amount in a range of from about about 0.001 wt % to about 5.0 wt %.

28. The method of claim 20 wherein the second linker is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt % to about 5.0 wt %.

29. A method of forming a product solution from a biologically derived oil source, the product solution having an oil phase and a water phase, comprising the steps of: providing at least one biologically derived oil source; contacting the at least one biologically derived oil source with an aqueous surfactant solution, the aqueous surfactant solution comprising: at least one surfactant having a head and a tail; and an aqueous solution; forming a product solution from contacting the aqueous surfactant solution with the at least one biologically derived oil source; and collecting the product solution.

30. The method of claim 29 wherein the aqueous surfactant solution further comprises; a first linker for lowering interfacial tension of the product solution created by contacting the biologically derived oil source and the aqueous surfactant solution; an electrolyte to give the aqueous surfactant solution a predetermined salinity; a second linker to decrease the equilibration time of the product solution created by contacting the biologically derived oil source and the aqueous surfactant solution.

31. The method of claim 30 wherein the first linker is a lipophilic linker that partitions near the tail of the surfactant to improve interaction of the surfactant with the water phase of the product solution.

32. The method of claim 30 wherein the second linker is a hydrophilic linker that partitions near the head of the surfactant to improve interaction of the surfactant with the oil phase of the product solution.

33. The method of claim 31 wherein the first linker is selected from the group consisting of a long chain alcohol, dodecanol, decanol, any alcohol with greater than 8 carbons, glycerol monoleate, sophorolipids, surfactants with a hydrophilic-lipophillic balance (HLB) less than 5, and combinations thereof.

34. The method of claim 32 wherein the second linker is selected from the group consisting of polyglucoside, sodium mono- and dimethyl naphthalene sulfonate, xylene sulfonate, surfactants with a HLB greater than 12, and combinations thereof.

35. The method of claim 29 wherein the at least one surfactant is a conventional surfactant selected from the group consisting of anionic, cationic, nonionic, amphoteric zwitter ionic, triblock copolymers, and combinations thereof..

36. The method of claim 29 wherein the at least one surfactant is an extended surfactant selected from the group consisting of a linear alkyl-polypropoxylated-sulfate, a linear alkyl-polypropoxylated- ethoxylated-sulfate, and combinations thereof.

37. The method of claim 36 w herein the at least one extended surfactant is present in the aqueous surfactant solution in an amount in a range of from about 0.01 wt % to about 5.0 wt %.

38. The method of claim 30 wherein the first linker is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt % to about 5.0 wt %.

39. The method of claim 30 wherein the second linker is present in the aqueous surfactant solution in an amount in a range of from about 0.001 wt % to about 5.0 wt %.

40. The method of claim 29 wherein the biologically derived oil source is selected from the group consisting of oilseeds, algae, red cedar, eastern cedar, tea trees, Pongamia pinnata, and combinations thereof.

41. The method of claim 29 further comprising the step of separating the oil phase from the product solution.

42. The method of claim 41 further comprising the step of separating any biologically derived oil source byproduct from the product solution.

43. The method of claim 29 further comprising the step of separating the water phase from the product solution and recycling it back to be contacted with the biologically derived oil source to produce additional product solution.

44. The method of claim 29 wherein the step of forming a product solution from contacting the aqueous surfactant solution with the at least one biologically derived oil source is done at ambient temperature and ambient pressure.