NZ625744B2 - Dissipative surfactant aqueous-based drilling system for use in hydrocarbon recovery operations from heavy oil and tar sands - Google Patents

Abstract

water-based drilling fluid which includes an aqueous fluid and a water-soluble dissipative surfactant composition is described, wherein the dissipative surfactant composition includes at least one fatty acid or ester derivative of a plant or vegetable oil. Also described are methods of using such aqueous-based drilling fluids including the dissipative surfactant composition as described in hydrocarbon recovery operations associated with oil/tar sand, where such fluids act to increase the dispersant qualities of hydrocarbons within the oil/tar sand, and where such fluid exhibit a reduced coefficient of friction. aqueous-based drilling fluids including the dissipative surfactant composition as described in hydrocarbon recovery operations associated with oil/tar sand, where such fluids act to increase the dispersant qualities of hydrocarbons within the oil/tar sand, and where such fluid exhibit a reduced coefficient of friction.

Description

DISSIPATIVE SURFACTANT AQUEOUS-BASED DRILLING SYSTEM FOR USE IN ARBON RECOVERY OPERATIONS FROM HEAVY OIL AND TAR SANDS CROSS REFERENCE TO RELATED ATIONS This application claims priority to U.S. Provisional patent application serial number 61/562,283, filed November 21, 2011, the contents of which are incorporated herein in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention.

The inventions disclosed and taught herein relate generally to components of well bore fluids and muds, and more specifically are related to water-based drilling fluids and components therein which are suitable for use in oil/tar sand formations.

Description of the Related Art.

When drilling or completing wells in earth formations, various fluids are typically used in the well for a variety of reasons. Common uses for well drilling and completing fluids include lubrication and cooling of drill bit g surfaces while drilling, ularly during drilling-in (drilling in a targeted iferous formation), transportation of "cuttings" to the surface, lling formation fluid pressure to prevent blowouts, maintaining well stability, cleaning the well, transmitting hydraulic horsepower to the drill bit, and otherwise treating the well or formation.

In numerous rotary drilling operations, the drilling fluid takes the form of a "mud"— that is, a liquid having solids suspended in it. The solids function to impart particularly desirable gical ties to the drilling fluid, while simultaneously increasing the density of the fluid in order to provide a suitable hydrostatic re at the bottom of the well.

Drilling systems are generally characterized as thixotropic fluid systems. That is, they exhibit low viscosity when sheared, such as when in circulation (as occurs during pumping or contact with the moving drilling bit). However, when the shearing action is , the fluid should be capable of suspending the solids it contains to prevent gravity separation. In addition, when the drilling fluid is under shear conditions and a free-flowing near-liquid, it must retain a sufficiently high enough viscosity to carry all unwanted particulate matter from the bottom of the well bore to the surface. The ng fluid formulation should also allow the cuttings and other unwanted particulate material to be removed or otherwise settle out from the liquid fraction.

Further, it is important that drilling fluids minimize the torque and drag that occurs in association with the drill string, particularly during the drilling operation itself.

There is an increasing need for drilling fluids having rheological properties to enable wells to be d while minimizing torque and drag, particularly in more challenging ions, such as oil/tar sand. Oil sand or tar sand, as they are generally referred to, more accurately termed bituminous sand, are a type of entional eum deposit. The sand contains lly occurring es of sand, clay, water, and a dense and extremely viscous form of petroleum technically referred to as bitumen (or colloquially "tar" due to its similar appearance, odor, and color). Oil/tar sand is found in large s in many countries throughout the world, but are found in extremely large quantities in both Canada and Venezuela, with other reserves being located in Kazakhstan and Russia. These types of formations often have unconsolidated sands, and exhibit highly varied porosity and permeability, which can cause high on on a drill string during drilling operations, resulting in excessive torque and drag on the drill string and drill bit, stuck pipe incidents, and shaker screen blinding, to name only a few.

Thus, historically, the majority of drilling operations in oil/tar sand and similarly difficult to drill formations have used oil- or hydrocarbon-based drilling muds, or have incorporated diesel or similar compounds as ants to counteract the ms in dealing with such formations.

While the use of such lubricants in the drilling fluids improves lubrication to such an extent that it permits the drilling of wells in difficult ions as well as vertically-deviated wells (e.g., horizontal wells) where torque, drag and the potential for pipe sticking on the drill string are significant, the lubricating characteristics of such fluids must be balanced with environmental considerations in using such hydrocarbon-based fluids.

At least some embodiments disclosed herein are directed to improved drilling and completion fluids and systems for use in hydrocarbon recovery operations, wherein the systems exhibit improved gical properties, particularly when the drilling operations are in oil/tar sand. It has been advantageously found that the ative surfactant described herein acts not only to lower the coefficient of friction, but also as a dispersant that generates a uniform drilling fluid mixture with improved flow properties due to its gglomeration/dispersive characteristics on oil/tar sand.

Any discussion of documents, acts, materials, devices, articles or the like which has been ed in the present specification is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the t disclosure as it existed before the priority date of each claim of this application.

BRIEF SUMMARY OF THE ION Disclosed herein is a method of treating a subterranean formation sing bituminous sand, the method comprising: providing a modified drilling fluid by mixing a dissipative tant composition with a water-based drilling fluid, and dispersing a portion of the bituminous sand by drilling a wellbore within the subterranean formation while circulating the modified drilling fluid through the wellbore, the dissipative surfactant composition ses (1) 20 % to 95 % of at least one fatty acid derived from a plant or fatty acid derivative derived from a plant and (2) an extreme pressure additive, the extreme pressure additive being a sulfur- or phosphorus-based derivative, or a combination of sulfur- and/or phosphorus-containing compounds, or a combination of such compounds that is polar and sterically small enough to ct with the metal surface of a piece of drilling equipment, and wherein the drilling fluid comprises water and a gelling agent.

Also disclosed herein is a water-based drilling fluid which includes an aqueous fluid, a gelling agent, an alkaline buffer, and a water-soluble, dissipative surfactant composition which es at least one fatty acid or ester tive of a plant or ble oil, and optionally an extreme pressure additive, is described, wherein the based drilling fluid is suitable for use in drilling oil/tar sand containing formations and exhibits reduced coefficient of friction teristics in the drilling fluid.

A water-based drilling fluid is also described, the drilling fluid comprising an aqueous fluid and a dissipative surfactant composition comprising at least one fatty vegetable oil or fatty acid d from a plant, an extreme pressure additive, and optionally at least one synthetic ester or diester. The fatty vegetable or plant oil in the dissipative surfactant composition may comprise at least one of a triglyceride, ricinoleic acid, linoleic acid, oleic acid, stearic acid, palmitic acid, dihydroxystearic acid, linolenic acid, and eicosanoic acid. The fatty acid may be a C14-C28 fatty acid. The plant source of the fatty vegetable oil or fatty acid may be selected from the group consisting of plants of the Brassica species, including canola and rapeseed, soy, corn, sunflower, cotton, cocoa, safflower, oil palm, coconut palm, flax, castor, peanut, wheat, oat, and rice, any of which may be naturally-occurring or transgenic (genetically-modified, such as to produce a higher amount of a specific fatty acid). The fluid may further comprise a number of additional, optional additives as riate, ing at least one of a buffering agent, a filtration control additive, and a gelling agent.

A method of treating a well bore extending into a ranean formation is also described, the method comprising the steps of mixing an aqueous fluid and a ative surfactant composition comprising one fatty vegetable oil or fatty acid d from a plant, an extreme pressure additive, and optionally at least one ester or diester, to form a water-based well bore fluid, and, thereafter using the water-based well bore fluid during a drilling operation.

A well bore fluid is also described, the fluid comprising an aqueous fluid and a dissipative surfactant composition comprising at least one ble oil, at least one extreme pressure and/or friction reducing additive, and optionally at least one ester or diester having from 8 to 30 carbon atoms. In further accordance with this embodiment, the dissipative surfactant composition contains an extreme pressure ve component that is non-halogenated and contains phosphorus, sulfur, or both.

A method of drilling a subterranean formation utilizing an aqueous based drilling fluid is also described, wherein the drilling fluid is comprised of an aqueous base fluid and a dissipative surfactant additive system, wherein the dissipative surfactant system comprises: a plant or vegetable oil or vegetable oil triglyceride obtained from naturally-occurring or genetically-modified plant species selected from the group consisting of Brassica, Helianthus, Glycine max, Zea mays, Crambe, and thes species; and a orus- or sulfur- containing on reducing or extreme pressure ve; and wherein the method includes adding an effective amount of the dissipative surfactant system to substantially reduce the coefficient of friction ed to a fluid absent the dissipative surfactant system.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE GS The following Figures form part of the present specification and are included to further demonstrate n s of the present invention. The invention may be better understood by reference to one or more of these Figures in combination with the detailed description of specific embodiments presented herein.

Figure 1 is an image of the oil/tar sand used in the testing of the compositions of the present disclosure.

Figure 2 is a photograph of the composition of Example 1 with 20 lb/bbl r sand, after dynamic aging.

Figure 3 is a photograph of the composition of Example 2, containing a ative tant in accordance with the present disclosure, after dynamic aging.

While the inventions disclosed herein are susceptible to various modifications and alternative forms, only a few specific embodiments have been shown by way of example in the gs and are described in detail below. The Figures and detailed descriptions of these specific embodiments are not intended to limit the breadth or scope of the inventive concepts or the appended claims in any manner. Rather, the Figures and detailed written descriptions are provided to illustrate the inventive concepts to a person of ordinary skill in the art and to enable such person to make and use the inventive concepts.

DETAILED DESCRIPTION The s described above and the n description of specific ures and functions below are not ted to limit the scope of what Applicants have invented or the scope of the appended claims. Rather, the Figures and written description are provided to teach any person skilled in the art to make and use the inventions for which patent protection is sought.

Those skilled in the art will appreciate that not all features of a commercial embodiment of the inventions are described or shown for the sake of clarity and understanding. Persons of skill in this art will also iate that the development of an actual commercial embodiment incorporating aspects of the present inventions will require numerous implementation-specific decisions to achieve the developer's ultimate goal for the commercial embodiment. Such implementation-specific decisions may include, and likely are not limited to, compliance with system-related, business-related, government-related and other aints, which may vary by specific implementation, location and from time to time. While a developer's s might be complex and time-consuming in an absolute sense, such s would be, nevertheless, a routine undertaking for those of skill in this art having benefit of this disclosure. It must be understood that the inventions disclosed and taught herein are susceptible to numerous and s modifications and alternative forms. Lastly, the use of a singular term, such as, but not limited to, "a," is not intended as ng of the number of items. Also, the use of relational terms, such as, but not limited to, "top," "bottom," "left," "right," "upper," "lower," "down," "up," " and the like are used in the written description for clarity in specific reference to the Figures and are not intended to limit the scope of the invention or the ed claims.

Applicants have created an improved aqueous-based drilling and tion fluid for use in hydrocarbon recovery operations, particularly those involving the presence of oil/tar sand, wherein the drilling and completion fluid includes an aqueous fluid and an environmentally friendly dissipative medium, optionally referred to herein as a "dissipative surfactant," wherein the dissipative tant includes at least one fatty acid or oil derived from a plant, particularly a fatty acid or oil derived from a ble, which may be transgenic or not (e.g., naturallyoccurring ), and at least one phosphorus or sulfur-containing extreme wear additive. In particular, it has been advantageously found that the inclusion of the dissipative surfactant composition displays anti-agglomeration/dispersive characteristics on oil/tar sand, thereby generating a uniform drilling fluid mixture with improved fluid flow properties and a reduced coefficient of friction.

Embodiments disclosed herein ularly relate to dissipative surfactants for use in aqueous, water-based re or drilling fluid formulations. In particular, embodiments described herein relate to aqueous wellbore fluid treating systems which se dissipative surfactant compositions in turn comprising fatty acids and ester derivatives of fatty acids found in plant oils, such as those from the family Brassica. In the following description, numerous details are set forth to provide an understanding of the t disclosure. However, it will be understood by those d in the art that the present disclosure may be practiced without these details and that us variations or modifications from the described embodiments may be possible.

In one embodiment, a water-based drilling fluid comprises an aqueous fluid, a ative surfactant composition, and optionally at least one of a buffering agent , alkaline buffer, and a gelling or viscosifying agent, as may be appropriate. The dissipative surfactant composition may comprise at least one fatty acid or fatty acid derivative, saturated or unsaturated, of either cis- or trans- geometry that is derived from a plant oil, preferably a food or vegetable oil. In another embodiment, a wellbore fluid may comprise an aqueous fluid and a dissipative surfactant composition, wherein the dissipative surfactant composition ses at least one fatty acid or fatty acid derivative, saturated or unsaturated, of either cis- or trans- geometry that is derived from a plant oil (naturally occurring or transgenic), preferably a food or vegetable oil, wherein the fatty acid or fatty acid derivative may comprise oleic acid, an oleic acid ester, a triglyceride, or a tive thereof. One of ordinary skill in the art would recognize that drilling or well bore fluids may also comprise various other additives, as appropriate, including biocides and the like.

Plant oil-based dissipative surfactant In accordance with one embodiment of the present sure, an aqueous (water-based) drilling fluid exhibits improved drilling characteristics, particularly in oil/tar sands, the fluid sing an aqueous fluid and a dissipative surfactant composition or system admixed with the aqueous fluid, the dissipative tant composition comprising a vegetable-based or plantbased oil (either natural or transgenic), hydrogenated or non-hydrogenated, or a synthetic triglyceride derived from such an oil, and at least one of a friction reducing/extreme pressure additive and a synthetic or natural diester. Preferably, the ative surfactant composition of the present disclosure is water soluble or substantially (e.g., at least 95 %, and preferably at least 98 - 99 % soluble in water or an aqueous solution) water soluble. r, the dissipative medium, or dissipative surfactant composition, is present in the water-based drilling or wellbore fluids described herein in an amount ranging from about 1 vol. % to about 10 vol. %, inclusive, including about 2 vol. %, about 3 vol. %, about 4 vol. %, about 5 vol. %, about 6 vol. %, about 7 vol. %, about 8 vol. %, and about 9 vol. %, as well as ranging within this range (e.g., from about 2 vol. % to about 8 vol. %, or from about 3 vol. % to about 6 vol. %), based on the total volume of the drilling fluid system.

As used herein, the term genic" refers to a "transgenic , which means a plant whose genome has been altered by the stable integration of recombinant DNA. A enic plant includes a plant regenerated from an ally-transformed plant cell and progeny transgenic plants from later generations or crosses of a transformed plant. As used herein "recombinant DNA" means DNA which has been a genetically engineered and constructed outside of a cell including DNA containing lly occurring DNA or cDNA or synthetic DNA. ary transgenic plants that are suitable for use with the compositions of the present disclosure include those cultivars of Brassica s, such as canola cultivars, that comprise an oleic acid value of 65% or higher (at least 85 % oleic acid (C18:1 ), and optionally less than 3 % linolenic acid (C18:3).

Generally, the dissipative surfactant of the present disclosure utilizes plant or ble oil fatty acids or esters thereof, glycerides or triglycerides (C5-C28) derived from plants or vegetable seeds. These natural oils typically contain C16 palmitic acid, and C18 stearic, oleic, ic, and nic acids - (C18:3) and gamma (C18:3), among others. The dissipative surfactant composition may be composed of from about 20% to 95% natural plant oil or a fatty acid, fatty acid ester, triglyceride, or glyceride ed therefrom. ably the oil is in the amount of up to or about 30, 40, 50, 55, 60, 65, 75, 80, 85 or 90% of the dissipative surfactant composition. More preferably the plant or vegetable oil is included in the dissipative medium of the s treating fluid in an amount up to or about 75 wt. or vol. % of the composition. The dissipative surfactant may also, ally comprise one or more esters or diesters, either synthetic or naturally ing, preferably esters or diesters having from 10 to 30 carbons (e.g., C10 - C30), inclusive, in an amount ranging from about 10 vol. % to about 50 vol. %, including about 20 vol. %, 30 vol. %, and 40 vol. %. Finally, and as will be ed herein, the dissipative surfactant may comprise one or more extreme pressure and/or friction reducing additives.

In one embodiment, a dissipative surfactant ition may include a plant oil derivative that is formed by on of at least one fatty acid derived from the plant oil (e.g., canola oil or an oil from Brassica, Helianthus, Glycine max, Zea mays, Crambe, and Limnanthes species) with at least one mono-, di-, tri-, or polyol to form a fatty acid ester derivative. Such fatty acids naturally ing in a plant-derived oil may include, but are not limited to, at least one of ricinoleic acid, oleic acid, stearic acid, ic acid, dihydroxystearic acid, linoleic acid, alpha-linoleic acid, gamma-linolenic acid, and eicosanoic acid (C20:0), as well as other saturated and rated fatty acids and fatty acid esters. The functional groups, such as hydroxyl groups (as on ricinoleic acid, palmitic acid, and stearic acid) and olefin functionalities may allow for further chemical functionalization of the fatty acid, and consequently further refinement of the physical properties of the compounds. Additionally, ester derivatives of fatty acids found in plants or vegetables (naturally occurring or transgenic) may be non-toxic and readily biodegradable, adding to their desirability for use in the dissipative surfactant compositions of the present disclosure. Suitable vegetable oils for use in the dissipative surfactant compositions of the present disclosure include for example, and without limitation, rapeseed (Brassica), sunflower (Helianthus), soybean (Glycine max), corn (Zea mays), crambe (Crambe), and foam (Limnanthes) oil. In one preferred aspect, canola oil (typically obtained from genus Brassica napus L. or Brassica campestris L., or a blend thereof, either natural or transgenic) is preferred for use.

The term ride" as used herein refers to glycerides that are derived from natural, particularly plant, sources, as well as to glycerides that are synthetically produced. Glycerides are esters of ol (a trihydric alcohol) and fatty acids in which one or more of the yl groups of glycerol are esterified with the yl groups of fatty acids containing from about 4 to about 75 carbon atoms and ably from about 6 to about 24 carbon atoms. The fatty acids can be saturated or unsaturated, linear, branched or cyclic monocarboxylic acids. Where three hydroxyl groups are esterified, the resulting glyceride is denoted as a "triglyceride." When only one or two of the hydroxyl groups are esterified, the resulting products are denoted as "monoglycerides" and "diglycerides," tively. Natural glycerides are mixed glycerides comprising triglycerides and minor amounts, e.g., from about 0.1 to about 40 mole percent, of mono- and diglycerides. Natural glycerides include, e.g., coconut, sunflower, and n (Glycine max) oils. Synthetically produced glycerides, in accordance with the present disclosure, are synthesized by a condensation reaction between glycerol and a fatty acid or mixture of fatty acids containing from about 6 to about 24 carbon atoms and obtained from a l or transgenic plant or vegetable source. The fatty acid can be a saturated or unsaturated, linear, branched, a cyclic monocarboxylic acid, or mixture thereof. The fatty acid itself can be derived from, for example, natural (or transgenic), i.e., plant / vegetable, sources as suggested above.

Examples include, but are not limited to, c, caprylic, capric, lauric, myristic, ic, stearic, arachidic, arachidonic, oleic, linoleic and , gamma-, and dihomo gamma-linolenic acids, and mixtures of any of the foregoing. The synthetically produced glycerides will contain from about 80 to about 100 mole percent triglycerides with the balance, if any, enting from about 0 to about 20 mole percent mono and diglycerides, present in admixture with triglycerides.

As ted above, the oil, fatty acid, or fatty acid derivative useful in formulating the dissipative surfactant itions of the present disclosure are derived from, for example, natural sources, i.e., those d from natural sources such as naturally-occurring plants and vegetables; transgenic plants and vegetables; and combinations thereof. Natural oils useful in the dissipative tant compositions of the present disclosure include, but are not limited to, coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, castor oil, rape oil, corn oil, beef tallow oil, whale oil, sunflower, cottonseed oil, linseed oil, tung oil, tallow oil, lard oil, peanut oil, canola oil, soya oil, and the like. Optionally, in accordance with select aspects of the disclosure, the oil can be synthetic oil based on or derived in part from a natural or transgenic oil, fatty acid, or fatty acid derivative. Such natural material based synthetic oils suitable for use herein refers to products produced by reacting carboxylic acids with glycerol, e.g., glycerol triacetate, and the like, to form glycerol esters. Suitable starting oils can contain triacylglycerols (TAGs), which contain three fatty acid chains esterified to a ol moiety and can be natural or synthetic. For example, TAGs such as triolein, trieicosenoin, or trierucin can be used as starting materials. TAGs are commercially available from a variety of commercial sources, for example, from Aldrich Chemical Company (St. Louis, MO.), or can be synthesized using standard techniques, such as, for e, from naturally-occurring tallow oil, palm oil, castor oil, cottonseed oil, corn oil, peanut oil, rapeseed oil (including canola oil), safflower oil, sesame oil, soybean oil, sunflower oil, olive oil, coconut oil, palm kernel oil, u oil, canola oil, soya oil, nut oils (e.g., almond oil), citrus oils (e.g., lemon oil) and the oils from the seeds of members of the citrus , oils from members of the Cucurbitaceae family (gourds, melons, pumpkins and es), and the like, as well as combinations of such oils, with canola oil (naturally derived or transgenic) being preferred for use herein.

The foregoing glycerol esters will contain from about C4 to about C75 and preferably contain about C6 to about C28 fatty acid esters, i.e., l fatty acid moieties, the number and type varying with the source of the oil. Fatty acids are a class of compounds containing a long hydrocarbon chain and a terminal carboxylate group and are terized as unsaturated or saturated depending upon r a double bond is present in the hydrocarbon chain. Therefore, an unsaturated fatty acid has at least one double bond in its hydrocarbon chain whereas a saturated fatty acid has no double bonds in its fatty acid chain. Examples of rated fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, oleic acid, linolenic acid, and the like. Examples of saturated fatty acids include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, c acid, arachidic acid, behenic acid, lignoceric acid, and the like.

The acid moiety may be supplied in a fully esterfied compound or one which is less than fully esterfied, e.g., glyceryl tri-stearate, or glyceryl di-laurate and glyceryl mono-oleate, respectively. It is particularly advantageous to employ plant derived oils, i.e., vegetable oils, as starting materials, as they allow the on products herein to be produced in a cost-effective manner. Suitable vegetable oils have a monounsaturated fatty acid t of at least about 50%, based on total fatty acid content, and include, for example, rapeseed (Brassica), sunflower (Helianthus), soybean (Glycine max), corn (Zea mays), crambe (Crambe), and foam (Limnanthes) oil. Canola oil (typically obtained from genus Brassica napus L. or Brassica campestris L., or a blend thereof), which has less than 2% erucic acid, is a particularly useful rapeseed oil. Oils having a monounsaturated fatty acid content of at least 70% are also particularly useful. The monounsaturated fatty acid content can be composed of, for e, oleic acid (C18: 1 ), eicosenoic acid (C20: 1 ), erucic acid (C22: 1 ), or combinations thereof.

Further, non-limiting examples of species to which the present disclosure is able include species of the genus Brassica, , and Beta. In one particularly advantageous embodiment, the dissipative medium can comprise at least one fatty vegetable oil or fatty acid obtained or derived from the seeds of small seeded vegetables. Non-limiting examples of species from which such fatty vegetable oil or fatty acids may be obtained include but are not limited to: Allium cepa; Allium porum; Brassica oleracea; Brassica campestris; Brassica napus; Beta vulgaris; and Daucus carota.

In one non-limiting embodiment of the present disclosure, the dissipative surfactant composition includes natural or enic canola oil or an oil from a Brassica species (naturally occurring or transgenic), or the mixture of fatty acids naturally occurring in such oil, that has been subjected directly to esterification with at least one mono-, di-, tri-, or polyol to form a mixture of fatty acid ester derivatives. In another embodiment, any combination of fatty acids including ricinoleic acid, oleic acid, stearic acid, palmitic acid, dihydroxystearic acid, ic acid, linolenic acid, or eicosanoic acid may be esterifed with at least one mono-, di-, tri-, or polyol.

In an optional aspect of the disclosure, at least one fatty acid derived from canola oil or an oil derived from a Brassica species of plant (natural or transgenic) may be reacted with at least one mono-, di-, tri-, or Polyol to form a fatty acid ester suitable for use in the dissipative s described herein. The reaction of at least one fatty acid with at least one mono-, di- tri-, or polyol may be conducted in a manner known by those skilled in the art. Such reactions may include, but are not limited to, Fischer (acid-catalyzed) esterification and acid-catalyzed transesterification, for example.

Friction reducer/extreme pressure additive.

In an exemplary embodiment of the present sure, as indicated above, the dissipative surfactant useful in the aqueous fluid compositions of the present disclosure ably includes one or more extreme pressure or on ng additives (referred to lently herein as me pressure additives"), which may be halogenated or nonhalogenated , and which preferably are water-soluble. In accordance with certain aspects of the present disclosure, the extreme pressure additive is a sulfur- or phosphorus-based derivative, or a combination of sulfur- and/or phosphorus-containing compounds (e.g., a thiocarbamate and a phosphate), or a combination of such compounds that is polar and ally small enough to ct with the metal surface of a piece of drilling ent (e.g., drill string, drill bit, etc.), and preferably one that is environmentally responsible.

The term 'phosphorous-based' e pressure additive means a phosphorus-based derivative of an organic compound, such as phosphorus-based amine phosphates or phosphorusbased alkyl or alcohol ates, including alkylamine or alkanolamine salts of phosphoric acid, butylamine phosphates, long chain alkyl amine phosphates, organophosphites, propanolamine phosphates, or other hydrocarbon amine ates, ing triethanol, monoethanol, dibutyl, dimethyl, and opropanol amine phosphates. The phosphorus-based derivative may be also an ester including thioesters or amides of phosphorous containing acids.

Additionally, the organic moiety from which the phosphorous nd is derived may be an alkyl, alcohol, phenol, thiol, thiophenol or amine. The three organic residues of the phosphate compound may be one or more of these or combinations. In select aspects of the present disclosure, alkyl groups with 1 to 12 carbon compounds are suitable. A total carbon content of 2 to 12 carbon atoms is particularly suitable. The phosphorous based compound may be a phosphorous oxide, phosphide, phosphite, phosphate (including mono- and di-hydrogen phosphates), osphate and thiophosphate, and may be halogenated (e.g., containing one or more chlorine atoms) or non-halogenated.

In accordance with select aspects of the present sure, dissipative surfactant compositions and systems may include extreme re ves/friction reducing compounds that are water-based or water-soluble. In example, suitable water-soluble extreme pressure additives include ethoxylated alkylalcohols, and particularly the alkali metal salt of a phosphate ester of an ethoxylated alkylalcohol.

The term i metal salt" as used herein refers to lithium, sodium, or potassium salts, preferably the sodium or potassium salts.

The term "alkylalcohol" as used herein means C6-C24 linear or branched alkylalcohols such as, without limitation, butanol, sec-butanol, isobutanol, 3-methylbutanol, pentanol, 2- pentanol, l, 2-hexanol, 2-methylpentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-octanol, 2-ethylhexanol, 2,4,4-trimethyl-1 -pentanol, nonanol, 2,6-dimethylheptanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol, canol, 2,4,4-trimethylpentanol, and the like. The alkylalcohols es lated alcohols, which includes alkoxylated monohydric alcohols or alkoxylated polyhydric alcohols.

The alkoxy alcohols are generally produced by treating an alcohol with an excess of an alkylene oxide such as ethylene oxide or propylene oxide. Exemplary alkylalcohols include ethyoxylated linear ls, which may be ented by the general structural formula CH3(CH2)xCH2(OCH2CH2)nOH where x is an integer ranging from 4 to 18 (inclusive), and n is an r g n 1 and 11 (inclusive). An exemplary, non-limiting phosphorus-containing extreme re additive suitable for use in the compositions of the present disclosure is a potassium phosphate salt of an lcohol, such as for example alpha-isodecyl-omega-hydroxy-poly(oxy-1,2-ethanediyl) phosphate, potassium salt.

The extreme pressure additive may also equivalently be a sulfur-based derivative such as sulfurized fatty esters, sulfurized hydrocarbons, sulfurized triglycerides, alkyl polysulfides and combinations.

The dissipative surfactant composition suitable for use with the aqueous drilling or completion fluid may be composed of from about 2% to 30% extreme pressure additive by weight of the drilling fluid composition, or in an amount from about 0.1 to about 20 % by weight of the dissipative surfactant composition. Preferably, the extreme pressure additive is present in an amount of up to or about 0.5, 1, 2, 3, 4, 5, 10, 15, or 20 % of the dissipative surfactant composition. In some embodiments, the ratio of the vegetable oils or triglycerides to the polar non-chlorine extreme pressure additive is in the range of from about 1:1.5 to about 48:1, as riate.

Drilling/wellbore fluid formulation In one embodiment of the present disclosure, a water-based drilling fluid or drilling fluid system ses an aqueous fluid, a dissipative surfactant composition comprised of a plant-derived oil or triglyceride such as canola oil or its components as described above, and an extreme pressure/friction reducing additive, and optionally one or more synthetic diesters having from 8 (or less) to 28 carbon atoms, the aqueous fluid system further and optionally containing at least one of a weighting agent, a gelling agent/viscosifier, an alkaline buffer, and a filtration l ve. Exemplary synthetic diesters suitable for use in the present dissipative medium compositions include but are not d to alkyl, isoalkyl, cycloalkyl, aryl, aryl-substituted alkyl, or ring-opened alkyl diesters, having from either from 8 to 28 carbon atoms, or in the alternative, 8 or fewer carbon atoms, depending on the specifics of the formulation. Such tic diesters are the reaction product of monohydroxy alcohols and dicarboxylic acids.

In an exemplary formulation in accordance with aspects of the t disclosure, the dissipative surfactant composition comprises a natural or transgenic plant or vegetable oil, or carboxylic acid (such as oleic or ricinoleic acid), or a fatty acid (such as a triglyceride) derived or obtained from a naturally occurring or transgenic plant or vegetable species in an amount ranging from about 30 wt. % to about 85 wt. %; a phosphorus- or sulfur-containing extreme pressure additive in an amount ranging from about 0.1 wt. % to about 20 wt. %; an optional synthetic ester or diester in an amount g from 0 wt. % to about 15 wt. %; an optional polymer in an amount ranging from 0 wt. % to about 25 wt. %; and an optional emulsifier in an amount ranging from about 0 wt. % to about 30 wt. %. In accordance with certain s of the disclosure, the dissipative surfactant composition advantageously exhibits a flash point of greater than 200 °F (93 °C), and preferably greater than about 300 °F (149 °C).

The aqueous fluid includes substantially any aqueous fluid that does not adversely react with the constituents of the fracturing fluid, the subterranean formation, or the fluids present therein. The aqueous fluid can e, for example, fresh water, natural brines, or artificial brines, such as potassium chloride solutions, sodium chlorides solutions, and the like.

The aqueous fluid of the well bore fluid may include at least one of fresh water, sea water, brine (e.g., NaCl, KCl, NaBr, KBr, CaCl2, CaBr2, ZnBr2, ZnCl2, CaCl2/CaBr2/ZnBr2, , KCO2H, and CsCO2H brines), mixtures of water and water-soluble organic compounds and mixtures thereof. For example, the aqueous fluid may be formulated with mixtures of desired salts in fresh water. Such salts may include, but are not limited to alkali metal des, hydroxides, or ylates, for example. In various embodiments of the drilling fluid disclosed herein, the brine may include seawater, s solutions n the salt concentration is less than that of sea water, or aqueous ons wherein the salt concentration is greater than that of sea water. Salts that may be found in seawater include, but are not limited to, sodium, calcium, aluminum, ium, potassium, strontium, and lithium, salts of chlorides, bromides, carbonates, iodides, chlorates, bromates, formates, nitrates, oxides, phosphates, sulfates, tes, and des. Salts that may be incorporated in a given brine include any one or more of those present in l seawater or any other organic or inorganic dissolved salts.

Additionally, brines that may be used in the drilling fluids disclosed herein may be l or synthetic, with synthetic brines g to be much simpler in constitution. In one embodiment, the density of the drilling fluid may be controlled by increasing the salt concentration in the brine (up to saturation). In a particular embodiment, a brine may include halide or carboxylate salts of mono- or divalent cations of metals, such as cesium, potassium, calcium, zinc, and/or sodium.

In one embodiment, the water-based ng fluid system of the present disclosure may further and optionally include one or more weighting agents or materials. Weighting materials suitable for use in the fluid compositions disclosed herein are preferably solid-phase materials selected from the group consisting of ite (PbSO4), barite (BaSO4) and other bariumcontaining minerals or materials, calcite (CaCO3), celestite/celestine (SrSO4), crocoite (PbCrO4), hematite (Fe2O3), ilmenite 3), or combinations thereof. The quantity of such material added, if any, may depend upon the desired density of the final composition. lly, a weighting agent is added to result in a drilling fluid density of up to about 24 pounds per gallon.

In another embodiment, the water-based drilling fluid may include one or more gelling agents. The gelling agents suitable for use in the fluids disclosed herein may include both highgravity and avity solids, the latter of which may e both active , such as clays, polymers, and combinations thereof, and inactive solids. In a non-limiting aspect of the disclosure, the g agent may be any appropriate clay, including, but not limited to, palygorskite-type clays such as sepiolite, attapulgite, and combinations thereof, smectite clays such as hectorite, montmorillonite, kaolinite, saponite, bentonite, and ations thereof, Fuller's earth, micas, such as muscovite and phologopite, as well as synthetic clays, such as laponite. The g agent may also be a water-soluble polymer which will hydrate in the treatment fluids described herein upon addition. Suitable soluble polymers which may be used in these treatment fluids include, but are not limited to, synthesized ymers, such as n gum, cellulose derivatives, naturally-occurring polymers, and/or derivatives of any of these water-soluble polymers, such as the gums derived from plant seeds.

Polymeric fluid loss control additives used in well drilling and servicing fluids are socalled water-soluble polymers including atinized starch, starch derivatives, cellulose derivatives, lignocellulose derivatives, and synthetic polymers. Representative starch derivatives include: hydroxyalkyl starches such as hydroxyethyl starch, hydroxypropyl starch, hydroxypropyl carboxymethyl , the slightly crosslinked derivatives thereof, and the like; ymethyl starch and the slightly crosslinked derivatives thereof; cationic starches such as the tertiary amnioalkyl ether derivatives of , the slightly crosslinked derivatives thereof, and the like. Representative cellulose derivatives e low lar weight ymethyl cellulose, and the like. entative lignocellulose derivatives include the alkali metal and alkaline earth metal salts of lignosulfonic acid and graft copolymers thereof. Representative synthetic polymers include vinyl sulfonate copolymers, and polymers containing other sulfonate monomers.

Optionally, but preferably, the fluid compositions of the present disclosure may contain an alkaline buffer additive. The alkaline buffer may be any ne particulate material having a low water solubility which will react with acids to decrease the acidity of the .

Representative alkaline buffers are magnesium oxide, calcium oxide, zinc oxide, calcined dolomite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, hydrated dolomitic lime (calcium/magnesium hydroxide), and the like. In accordance with the present disclosure, the fluids should exhibit measured pH's in the range from about 3.0 to about 11.0. Brines ning zinc bromide should have a pH less than about 6.0 as is well known in the art. Although the actual pH's of highly concentrated salt solutions cannot be tely read using a pH meter, the relative pH's of several different highly concentrated salt solutions may be accurately compared.

Thus, the measured pH's of such highly concentrated solutions become a reliable monitoring method for determining the relative acidity of the fluids involved. The measured pH's are determined with a standard pH meter, the electrode of which is inserted into the on to be measured. As used herein, the term "measured pH" refers to pH's determined in the foregoing manner. Where it is necessary to adjust the measured pH, the adjustment may be carried out at substantially any time in accordance with the present disclosure.

The fluids of the present disclosure may contain other functional additives to impart specific properties to the fluids. Thus the fluids may contain lost circulation materials, corrosion inhibitors, anti-oxidants, oxygen scavengers, ng agents, polymer breakers, shale inhibitors, supplemental filtration control ves, supplemental viscosifiers, emulsifiers, rs, and the like. In additions, the fluids may also, optionally contain one or more anti-microbial/biocidal agents having water solubility, in any appropriate amount. Exemplary, suitable biocidal agent for use with the itions and systems of the present disclosure are BIO-KLEEN® and BioBAN™ P-1487, both available from the Dow Chemical Company (Midland, MI, USA).

In one embodiment, a method of ng a well bore comprises mixing an aqueous fluid comprising at least one of an alkaline buffer, a gelling agent, and a dissipative surfactant system as described herein. The dissipative surfactant comprises at least one fatty acid or one ester derivative of at least one fatty acid d from a plant or ble oil, such as canola oil or the like, to form a water-based well bore fluid. The water-based well bore fluid may then be used during a drilling ion. The fluid may be pumped to the bottom of the well through a drill pipe where the fluid emerges through ports in the drilling bit, for example. In one embodiment, the fluid may be used in conjunction with any drilling operation, which may include, for example and without limitation, vertical drilling, ntal drilling, extended reach drilling, and directional drilling. One skilled in the art would recognize that water-based drilling muds and ng fluids may be prepared with a large variety of formulations. Specific formulations may depend on the state of drilling a well at a particular time, for example, depending on the depth and/or the composition of the formation, as well as the temperature of the formation. The aqueous ng mud and fluid compositions described herein may be d to provide improved water-based drilling muds under conditions of high ature and pressure, such as those encountered in deep wells.

Methods of use The above-described compositions are useful for treating oil and/or gas wells suspected of, or known to contain, oil/tar sand. Useful compositions include those comprising water or a similar aqueous base fluid, an alkaline buffer, and a dissipative surfactant including at least one fatty acid or fatty acid ester derived from, or ed from, a vegetable or plant.

The methods can comprise selecting an oil and/or gas well, and pumping one of the above described compositions into the well, or alternatively drilling an oil or gas well in a difficult formation, e.g., oil/tar sand, using an aqueous composition as described herein as at least a part of the drilling fluid. As a result of such methods, the dissipative surfactant composition within the aqueous composition ys anti-agglomeration/dispersive characteristics on oil/tar sand, thereby generating a uniform drilling fluid mixture with improved flow properties and a d coefficient of friction, or lubricity.

The lubricity of a drilling fluid is important for enhancing the economics of ng and completing difficult ng scenarios, such as high angle holes and formations with a high degree of r sand. Lubricity is a measure of the coefficient of on between a moving part and a surface in contact with the part. The lower the coefficient of friction, the greater the lubricity. The coefficient of friction, u, is defined as the ratio of the force, F, required to move an object in contact with a surface to the force, W1, pushing downward or perpendicular to the object: u = F/W1. The coefficient of friction may alternatively and equivalently be called the friction coefficient, friction factor, or the lubricity coefficient. The lubricity of a ng fluid is a measure of the mud's ability to lower torque and drag forces.

In accordance with embodiments of the t disclosure, the aqueous-based drilling system compositions comprising a dissipative surfactant composition substantially reduces the coefficient of friction (and increases the lubricity) compared to a fluid absent the dissipative surfactant system. In accordance with some s, the instant compositions can reduce the coefficient of friction of an aqueous drilling fluid by an amount ranging from about 45 % to about 85 %, and more preferably by an amount ranging from about 50 % to about 75%, compared to an aqueous-based fluid that does not contain a dissipative surfactant system in accordance with the present disclosure. The drilling fluid s of the present disclosure may also exhibit other advantageous and synergistic effects on a hydrocarbon-recovery drilling system, ing reducing the torque and/or drag associated with the use of a drill bit in penetrating subterranean formations.

The pumping can be performed in a single pumping event, multiple pumping events, or as a continuous g process. The well can be d in," allowing the compositions to contact the well for a period of time during which additional pumping or drilling is not performed.

In one embodiment, a method of treating a well bore comprises mixing an s fluid sing at least one of a weighting agent and a gelling agent, and a ative surfactant composition or system. The dissipative surfactant system comprises at least one fatty acid or fatty acid derivative derived from a plant or vegetable oil (transgenic or nontransgenic /naturally-occurring) and an extreme pressure additive to form an aqueous water-based wellbore fluid, the ative surfactant system being ntially (greater than 90 %, and preferably greater than 95%) soluble in water, optionally as an emulsion. The based wellbore fluid may then be used during a drilling operation. The fluid may be pumped down to the bottom of the well through a drill pipe, where the fluid emerges through ports in the drilling bit, for example. In one embodiment, the fluid may be used in conjunction with any drilling ion, which may include, for e, vertical drilling, extended reach drilling, and directional drilling. Preferably, in accordance with the present disclosure, the drilling operation involves oil/tar sand or an oil/tar sand ion. One skilled in the art would recognize that water-based drilling fluids, systems, and muds may be prepared with a large variety of formulations. Specific formulations may depend on the state of ng a well at a particular time, for example, depending on the depth and/or the composition of the formation. The drilling fluid compositions and s described above may be adapted to provide improved waterbased drilling fluids under ions of high ature and re, such as those encountered in deep wells.

The following examples are included to demonstrate preferred embodiments of the present disclosure. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor(s) to function well, and thus can be ered to constitute preferred modes. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the scope of the invention.

Examples Example 1 : ation and Evaluation of Control Fluid System.

A control drilling and completion fluid system was prepared by admixing 0.96 bbl fresh water, 4.0 lb/bbl of l-Ultra™ (xanthan gum ymer and derivatized starch which acts as a gelling/filtration control agent), 4.0 lb/bbl FL-7 Plus® (a stabilized non-ionic derivatized starch that controls high temperature-high pressure filtrate loss), 1.0 lb/bbl pH Buffer, (magnesium oxide alkaline buffer), 8.0 lb/bbl Ultra Carb 2, (sized calcium carbonate weighting agent, D-50 le size of 2 microns), 30.0 lb/bbl Ultra Carb 20 (sized calcium carbonate weighting agent, D-50 particle size of 20 microns), and 20.0 lb/bbl of oil/tar sand. Thixsal- Ultra™, FL-7 Plus®, pH Buffer, Ultra Carb 2, and Ultra Carb 20 are manufactured and distributed by TBC-Brinadd (Houston, TX, USA). Following mixing, viscosities at various shear rates, coefficients of friction, and high temperature-high re filtrates were determined initially after mixing, and after dynamic aging at 150 °F for 16 hours using API standards. The data is presented in Tables A - D.

Example 2: Preparation and Evaluation of Dissipative Surfactant System of the Invention.

A drilling and completion fluid system was prepared by admixing 0.96 bbl of fresh water, 4.0 lb/bbl of Thixsal-Ultra™ (xanthan gum biopolymer and tized starch which acts as a gelling/filtration control agent), 4.0 lb/bbl FL-7 Plus® (a stabilized, non-ionic derivatized starch that controls high temperature-high pressure filtrate loss), 1.0 lb/bbl pH Buffer (magnesium oxide ne buffer), 8.0 lb/bbl Ultra Carb 2 (sized calcium carbonate weighting agent, D-50 particle size of 2 microns), 30.0 lb/bbl Ultra Carb 20 (sized calcium carbonate weighting agent, D-50 particle size of 20 microns), 20.0 lb/bbl of oil/tar sand, and 3%/vol. Bio- Stable (exemplary dissipative tant ition of the t disclosure, ctured for use herein by ProOne Inc., Costa Mesa, CA). Thixsal-Ultra™, FL-7 Plus®, pH Buffer, Ultra Carb 2, and Ultra Carb 20 are manufactured and distributed by TBC-Brinadd (Houston, TX, USA). Following mixing, viscosities at various shear rates, coefficients of friction, and high temperature-high re filtrates were determined initially after mixing, and after dynamic aging at 150 °F for 16 hours using API standards. That is, the initial fluid properties were measured before the samples were dynamically aged (hot rolling ovens to simulate downhole conditions) in a pressurized cell (to avoid boiling). Fluid properties were also measured after the aging process to monitor the effect of temperature during time on the samples. The aging temperature was the same as the maximum reservoir temperature. The data is presented in Tables A - D.

Table A: Initial Viscosity ison.

All ities recorded at 76 °F. Example 1 = the control fluid system; example 2 = the dissipative surfactant system.

Table B: Dynamic Aged Viscosity Comparison.

Dynamic aging was carried out at 150 °F for 16 hours; viscosities were recorded at 76 °F; example 1 = the control fluid system; e 2 = the dissipative surfactant system.

The test results for Examples 1 and 2 illustrate the ability of the compositions described herein to produce substantial changes in the viscosity of well drilling and completion systems across a broad range of shear rates. Table A shows that a composition containing 3%/vol. dissipative surfactant will disperse the oil/tar sand (Figure 1) and reduce the l viscosity by 3.6% to 30.9%, and the dynamic aged viscosity by 17.2% to 58.3% at shear rates of 1,022 sec-1 and 0.0636 sec-1, respectively. The data associated with the dynamic aged fluid samples is shown in Figures 2 and 3. Figure 3 shows complete dispersion in the dynamically aged fluid containing a ition including a dissipative surfactant composition in accordance with the present disclosure, as exhibited by the substantially homogenous and uniform fluid with no residual r sand adhering to the sides of the glass container, compared to the ted fluid shown in Figure 2 which shows the r sand being non-dispersed and the untreated fluid being ogenous.

Table C: Coefficient of Friction ison. 1Aged at 150 °F for 16 hours.

The control fluid system (Example 1) and the dissipative surfactant system (Example 2) at both the initial stage, and after dynamic aging (150 °F for 16 hours), were tested on a Baroid lubricity meter at 76 °F. The lubricity coefficient (coefficient of friction) of the samples was calculated and recorded in Table C. The results in Table C demonstrate that a composition containing 3%/vol. dissipative surfactant will reduce the coefficient of friction by 71.0% on the sample initially after mixing, and 52.6% on the sample that was dynamically aged at 150 °F for 16 hours.

Table D: Filtrate Loss Comparison.

Filtration was conducted at 150 °F and 500psi for 30 minutes; the tion media was a 10 Darcy aloxite disk; dynamic aging was carried out at 150 °F for 16 hours; viscosities were recorded at 76 °F; example 1 = the control fluid system; example 2 = the dissipative surfactant system.

The results in Table D show that a composition containing . dissipative surfactant will reduce the filtrate loss by 16.7% initially after mixing, and 6.3% on the sample that was dynamically aged at 150 °F for 16 hours.

Other and further embodiments can be devised without departing from the spirit of Applicant's invention. For example, additives other than those recited herein may be included, and further enhance the effects of the instant compositions due to a synergistic effect. Further, the various methods and embodiments of the s disclosed herein can be included in combination with each other to e variations of the disclosed methods and embodiments. sion of singular elements can include plural elements and vice-versa.

The order of steps can occur in a variety of sequences unless otherwise specifically limited. The s steps described herein can be ed with other steps, interlineated with the stated steps, and/or split into le steps. rly, elements have been described functionally and can be embodied as te components or can be combined into components having multiple functions.

The inventions have been described in the context of red and other embodiments and not every embodiment of the invention has been described. Obvious modifications and alterations to the described embodiments are available to those of ordinary skill in the art. The sed and undisclosed embodiments are not intended to limit or restrict the scope or applicability of the invention conceived of by the Applicants, but rather, in conformity with the patent laws, Applicants intend to fully protect all such modifications and ements that come within the scope or range of equivalent of the following claims.

Claims (9)

What is claimed is:

1. A method of treating a subterranean formation comprising bituminous sand, the method comprising: providing a modified drilling fluid by mixing a dissipative surfactant composition with a water-based drilling fluid, and dispersing a portion of the bituminous sand by drilling a wellbore within the subterranean formation while circulating the modified drilling fluid through the wellbore, the dissipative surfactant composition comprises (1) 20 % to 95 % of at least one fatty acid derived from a plant or fatty acid derivative derived from a plant and (2) an e pressure additive, the extreme pressure additive being a sulfur- or phosphorus-based derivative, or a combination of sulfur- and/or phosphorus-containing compounds, or a combination of such compounds that is polar and sterically small enough to interact with the metal surface of a piece of drilling ent, and wherein the drilling fluid comprises water and a gelling agent.

2. The method of claim 1, wherein the at least one fatty acid is ricinoleic acid, linoleic acid, oleic acid, stearic acid, palmitic acid, dihydroxystearic acid, lenolenic acid, or noic acid.

3. The method of claim 1, wherein the fatty acid derivative is an ester.

4. The method of claim 3, wherein the ester is derived from at least one of a mono-, di-, tri-, and polyol.

5. The method of claim 3, wherein the ester is derived from sorbitan or pentaerythritol.

6. The method of any one of the ing , wherein the modified drilling fluid comprises about 1 vol. % to about 10 vol. % of the dissipative surfactant ition.

7. The method of any one of the preceding , wherein the modified drilling fluid comprises about 1 vol. % to about 5 vol. % of the dissipative surfactant composition.

8. The method of any one of the preceding claims, n the dissipative surfactant composition comprises up to about 75 wt. % fatty acid or fatty acid derivative.

9. The method of any one of the preceding claims, wherein the plant is Allium cepa, Allium porum, Brassica oleracea, Brassica campestris, Brassica napes, Beta vulgaris, or Daucus carota.