Branched amino acid surfactant for oil and gas production

Abstract

Branched surfactants for use in formulations and processes suitable for hydrocarbon recovery, including formulations suitable for fracking, enhanced oil and / or gas recovery, and bio-based oil recovery and / or production.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to Provisional Patent Application No. 63 / 051,192, filed July 13, 2020, which is hereby incorporated by reference in its entirety.

[0002] The present disclosure relates to branched surfactants for use in the production and recovery of hydrocarbons, including oil and gas from wells and oil from biobased processes. Such branched surfactants can include derivatives of amino acids, which derivatives have surfactant properties.

Background Art

[0003] Surfactants (molecules having surfactant properties) are widely used in the commercial production of oil and natural gas. These formulations can include a variety of liquids, emulsions, and foams used in the recovery of hydrocarbons from soil and from biobased sources. Both oil and natural gas have been found to contact water or water - soluble substrates, and thus surfactants can be included in the formulations to improve the recovery of oil and / or gas. Ideally, the formulations for such production and recovery processes are easy to manufacture, deploy, and, in practical cases, reuse.

[0004] Surfactants can be non - charged, zwitterionic, cationic, or anionic. In principle, any surfactant classification (e.g., cationic, anionic, non - ionic, zwitterionic) is suitable, but it is possible for the formulation to include combinations of two or more surfactants from two or more surfactant classifications.

[0005] Surfactants are often amphiphilic molecules having a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can adsorb at interfaces, such as the interface between two liquids, a liquid and a gas, or a liquid and a solid. In systems containing relatively polar and relatively non-polar components, the hydrophobic tail preferentially interacts with the relatively non-polar component, while the hydrophilic head preferentially interacts with the relatively polar component. In the case of the interface between water and oil, the hydrophilic head group preferentially enters the water, while the hydrophobic tail preferentially enters the oil. When added to only the water-gas interface, the hydrophilic head group preferentially enters the water, while the hydrophobic tail preferentially enters the gas. The presence of a surfactant interrupts at least a portion of the intermolecular reactions between water molecules and replaces at least a portion of the intermolecular reactions between water molecules with generally weaker interactions between at least a portion of the water molecules and the surfactant. This can lower the surface tension and also serve to stabilize the interface.

[0006] At sufficiently high concentrations, surfactants can form aggregates that serve to limit the exposure of the hydrophobic tails to polar solvents. One such aggregate is the micelle. In a typical micelle, the molecules are arranged in a spherical shape, with the hydrophobic tails of the surfactant preferentially located inside the sphere and the hydrophilic heads of the surfactant preferentially located outside the micelle, where the heads preferentially interact with the more polar solvent. The effects that a given compound has on surface tension and the concentration at which micelles form can serve as defining characteristics of the surfactant.

[0007] The development and production of crude oil from an oil-bearing formation can include up to three phases: primary, secondary, and tertiary (or enhanced) recovery. During primary recovery, natural energy (e.g., water, gas) present in the formation, and / or gravity pushes the oil into the production wellbore. As oil is produced from the oil-bearing formation, the pressure and / or temperature within the formation can decline. Artificial lift techniques (e.g., pumps) can be used to bring the oil to the surface. Typically, only about 10 percent of the original oil in place (OOIP) of the reservoir is produced during primary recovery. Secondary recovery techniques are used to extend the production life of an oilfield and generally include the step of injecting a displacing fluid, such as water (waterflooding), to displace the oil and push it into the production wellbore.

[0008] Secondary recovery techniques typically result in an additional recovery of 20 to 40 percent of the OOIP of the reservoir. However, even if waterflooding is continued indefinitely, typically more than half of the OOIP remains unrecovered. Low mixing efficiency between water and oil (due to high interfacial tension between water and oil), capillary forces in the formation, formation temperature, salinity of the water in the formation, composition of the oil in the formation, insufficient sweep of the water injected through the formation, and other factors contribute to inefficiency. Thus, with primary and secondary techniques, a significant amount of oil remains in the reservoir.

[0009] Since most of the easily producible oil has already been recovered from the oil fields, producers are using tertiary, or enhanced oil recovery (EOR), techniques which have the potential to recover from 30 to over 60 percent of the OOIP in the reservoir. Three main categories of EOR: thermal recovery, gas injection and chemical techniques are commercially successful. Thermal recovery introduces heat (e.g., steam injection) to lower the viscosity of the crude oil and improve its ability to flow through the reservoir. Gas injection uses nitrogen, carbon dioxide or other gases that expand in the reservoir to push additional oil into the production wells. Other gases that dissolve in the oil reduce viscosity and improve fluidity. Chemical techniques involve injecting surfactants (surfactant flooding) to reduce the interfacial tension that prevents or inhibits the movement of oil droplets through the reservoir, or injecting polymers that give the oil present in the formation more mobility to move more easily through the reservoir.

[0010] Chemical technology can be used before, during, or after implementing primary and / or secondary recovery technologies. Chemical technology can also supplement other EOR technologies. Surfactant flooding methods can include surfactant polymer (SP) flooding and alkaline surfactant polymer (ASP) flooding. In the SP flooding method, water and / or brine containing about 1 wt.% surfactant and -0.1 wt.% polymer is injected into the reservoir. The ASP flooding method includes alkali in addition to the components used in the SP flooding method. ASP systems typically contain about 0.5 to 1 wt.% alkali, -0.1 to 1 wt.% surfactant, and about 0.1 to 1 wt.% polymer. Typically, the SP or ASP flooding method is followed by injection of a displacement fluid, such as a water flood and / or a polymer "slug". The choice between SP and ASP depends on the acid number of the oil to be recovered, the concentration of divalent cations in the reservoir brine, the economics of the project, the ability to perform softening or desalination, and other factors. The alkali sequesters divalent cations in the formation brine, thereby reducing the adsorption of surfactant through the formation during displacement. The alkali also reacts with naphthenic acid naturally present in the crude oil to produce an anionic surfactant (sodium naphthenate soap) in situ in the formation. The use of relatively inexpensive alkali reduces surfactant retention, thus reducing the amount of surfactant required and, consequently, the overall cost. The alkali can also help to change the wettability of the formation to a more water-wet state and improve the water imbibition rate.

[0011] In another EOR technology, "wettability alteration", surfactants can be introduced into the reservoir and combined with a change in electrolyte concentration to displace adsorbed oil by causing spontaneous water imbibition on the reservoir rock. This technology does not necessarily require a low interfacial tension between the oil and the aqueous phase or the formation of a microemulsion phase. It also does not require good displacement fluid sweep efficiency and, thus, can be useful in carbonate reservoirs where fracturing can occur and which are typically not very compliant. The surfactants used in the SP and ASP flooding methods have also shown usefulness in wettability alteration.

[0012] After injection into an oil-bearing formation, the surfactant system sucks up crude oil and brine from the formation and forms a multiphase microemulsion in situ. Once completed, the microemulsion becomes immiscible with the reservoir crude and exhibits low interfacial tension (IFT) with the crude oil and brine. Commercial surfactant EOR processes achieve ultra-low IFT (i.e., less than 10 mN / m) to impart mobility to discontinuous crude oil droplets in the formation and create an oil bank where both oil and water flow as continuous phases. The IFT varies depending on salinity, surfactant composition, crude oil composition, formation temperature, and other variables. For anionic surfactants, there is an optimal salinity where the microemulsion solubilizes equal amounts of oil and water and the microemulsion exhibits approximately equal IFT with the oil and brine. Ultra-low IFT generally exists only within a narrow salinity range that overlaps with the optimal salinity for a given microemulsion.

[0013] As described by P. Zhao et al. ("Development of High-Performance Surfactants for Difficult Oils". SPE / DOE Improved Oil Recovery Symposium, Tulsa, Okla., April 2008, SPE 113432), "The selection of surfactants for enhanced oil recovery applications requires laboratory tests on crude oil from the target reservoir and can involve considerable effort to find suitable surfactants and other... components... such as polymers, electrolytes, co-surfactants, and co-solvents."

[0014] In the dry-grind ethanol process, yellow dent corn is ground, liquefied, and sent to a fermenter. Enzymes and yeast are added to convert starch to ethanol, which is subsequently distilled off. This leaves a slurry called total stillage waste. The total stillage waste, which contains a concentrated oil fraction, is then separated via centrifugation into a liquid fraction called low-viscosity stillage waste and a solid fraction called wet cake. A portion of the low-viscosity stillage waste is recycled to assist in the liquefaction of the ground corn, while the remainder is concentrated via evaporation into high-viscosity stillage waste (or syrup), which is dried and mixed with the wet cake to form a soluble matter-added dried distillers grains (DDGS) residue. This is sold as cattle feed and is a good source of protein.

[0015] Due to the concentrating effect that dry-grinding has on the oil fraction, the corn oil extracted from the high-viscosity stillage waste has become a co-product that is profitable in the ethanol industry. The removal of corn oil reduces the energy density of DDGS, but some studies suggest that the high oil content in DDGS interferes with milk production in dairy cows and leads to undesirable pork belly in pigs. Therefore, removing some of the oil can not only lead to a valuable co-product but also improve the quality of DDGS.

[0016] Current methods for extracting corn oil from high-viscosity stillage waste include solvent extraction (often hexane) and decantation. Hexane extraction is effective but energy-intensive and requires a large capital investment. Decantation requires little capital investment and has the potential to be just as effective as hexane extraction.

[0017] Decantation using centrifugation has the advantage of the density difference between the oil and the aqueous phase, which creates buoyancy in the oil suspended in the solution. Due to the buoyancy being strong enough to overcome the interfacial interaction and the surface friction acting on the oil, the individual oil droplets must be large enough to generate sufficient force. Current separation devices used in the industry can separate particles as small as about 20 micrometers in diameter. The success of current corn oil decantation is highly dependent on the upstream processing conditions. Processes using high temperatures, high or low pH, finer grinding, and long holding periods tend to exhibit increased oil yields. These harsh conditions may not be preferred methods for extracting oils consumed by humans or animals, and thus the conditions can negatively affect the nutritional and sensory properties of the final product.

Summary of the Invention

[0018] The present disclosure provides formulations useful for the extraction of oil and natural gas from wells and for several applications from mixtures of oil-based fuels and aqueous media used in biobased processes for producing hydrocarbon fuels such as bio-diesel. These productions can be formulated to include one or more surfactants from one or more surfactant classifications disclosed herein. The surfactants can be used as agents that improve the recovery and / or separation of hydrocarbons from environments containing emulsifiers, wetting agents, dispersants, and / or water.

[0019] The present disclosure provides surfactants for use in the production of oil and gas in the form of derivatives of amino acids having surface-active properties. The amino acids can be naturally occurring amino acids or synthetic amino acids, or they can be obtained via ring-opening reactions of molecules such as lactams, such as caprolactam. The amino acids can be functionalized to form compounds having surface-active properties. Characteristically, these compounds can have a low critical micelle concentration (CMC) and / or the ability to lower the surface tension of liquids.

[0020] The present disclosure relates to a fracturing fluid formulation comprising at least one surfactant, polymer, or viscoelastic surfactant of formula I:

[0021]

Chemical formula

[0022] (wherein R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C 1 to C 6 alkyl, and C 1 to C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 to C 12 alkyl, R 4 is C 3 to C 10 alkyl, the terminal nitrogen may be further substituted with R 5 , R 5 is selected from hydrogen, an oxygen atom, and C 1 to C 6 alkyl, and C 1 to C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride ion, bromide ion, iodide ion, and 4-methylbenzenesulfonate ion).

[0023] The present disclosure also relates to a fluid for enhanced oil recovery comprising at least one surfactant, polymer, or viscoelastic surfactant of formula I:

[0024]

Chemical formula

[0025] (wherein R 1 and R 2is hydrogen, an oxygen atom, and C 1 ~C 6 independently selected from alkyl, C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 ~C 12 alkyl, R 4 is C 3 ~C 10 alkyl, and the terminal nitrogen may be further substituted with R 5 , R 5 is hydrogen, an oxygen atom, and C 1 ~C 6 selected from alkyl, C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride ion, bromide ion, iodide ion, and 4-methylbenzenesulfonate ion) at least one surfactant, linear, crosslinked, and / or block copolymer, and / or an optional viscoelastic surfactant, and / or an optional cosurfactant.

[0026] The present disclosure provides a formulation for recovering biologically produced oil, having the formula I:

[0027] [Chemical formula]

[0028] (wherein R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C 1 ~C 6 alkyl, C 1 ~C 6The alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, n is an integer from 2 to 5 (including 2 and 5), and R 3 is C 5 ~C 12 alkyl, and R 4 is C 3 ~C 10 alkyl, and the terminal nitrogen may be further substituted with R 5 , and R 5 is hydrogen, an oxygen atom and C 1 ~C 6 alkyl selected from, and C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride ion, bromide ion, iodide ion and 4-methylbenzenesulfonate ion), at least one surfactant, and water. A formulation is also provided.

[0029] The present disclosure relates to a formulation for use in a mixture of a flacking fluid and oil or natural gas, having the formula I:

[0030]

Chemical formula

[0031] (wherein R 1 and R 2 are independently selected from hydrogen, an oxygen atom and C 1 ~C 6 alkyl, and C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, n is an integer from 2 to 5 (including 2 and 5), and R 3 is C 5 ~C 12 alkyl, and R 4 is C 3 ~C 10 alkyl, and the terminal nitrogen is R5 may be further substituted, and R 5 is selected from hydrogen, an oxygen atom, and C 1 ~C 6 alkyl, and C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, and an optional counter ion may be associated with the compound, and if present, the counter ion may be selected from the group consisting of chloride ion, bromide ion, iodide ion, and 4-methylbenzenesulfonate ion) at least one surfactant, and water, optionally containing a gas, further provides a formulation.

[0032] The other features and means for achieving them mentioned above in the present disclosure will become clearer and be better understood by referring to the following description of the embodiments in conjunction with the accompanying drawings.

Brief Description of the Drawings

[0033]

Figure 1

Figure 2A

Figure 2B

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Figure 4A

Figure 4B

Figure 5A

Figure 5B

Figure 6A

Figure 6B

Figure 7A

Figure 7B

Mode for Carrying Out the Invention

[0034] I. Definitions As used herein, the phrase "within any range using these endpoints" literally means that any range can be selected from any two of the values listed prior to such phrase, regardless of whether the value is at the lower limit of the enumeration or at the upper limit of the enumeration. For example, a pair of values can be selected from two lower limit values, two upper limit values, or a lower limit value and an upper limit value.

[0035] As used herein, the term "alkyl" means any saturated carbon chain that can be straight-chain or branched-chain.

[0036] As used herein, the phrase "surface active" means that the related compound is capable of reducing the surface tension of a medium in which it is at least partially dissolved and / or that the interfacial tension with other phases can be at least partially adsorbed at the liquid / vapor and / or other interfaces. The term "surfactant" can be applied to such compounds.

[0037] Regarding non-precise technical terms, the terms "about" and "approximately" can be used interchangeably to refer to measurements that include the defined measurement value and any measurement value reasonably close to the defined measurement value. A measurement value reasonably close to the defined measurement value deviates from the defined measurement value by a reasonably small amount that is understood and readily ascertainable by a person of ordinary skill in the relevant industry. Such deviation can be due to measurement error or, for example, minor adjustments made to optimize performance. When it is determined that it is not easy for a person of ordinary skill in the relevant industry to ascertain the value for such a reasonably small difference, the terms "about" and "approximately" can be understood to mean plus or minus 10% of the defined value.

[0038] The present disclosure provides formulations for use in hydrocarbon production and / or recovery. Such formulations include: fracturing fluids, improved oil recovery (IOR) injection fluids; formulations for increasing natural gas production; formulations for recovering bio-oil from sources such as distillation waste liquids; and those containing vegetables, fruits, and nuts.

[0039] II. Fracturing Fluids To recover hydrocarbons from a hydrocarbon-bearing subterranean formation, a wellbore is drilled into the formation to provide a flow path for hydrocarbons from a reservoir within the formation to the surface. However, a stimulation technique called hydraulic fracturing often requires improvement of the flow path and recovery of hydrocarbons from an oil or gas well.

[0040] In hydraulic fracturing, a particular fluid is pumped into the target formation at a rate that exceeds the rate at which it can be dispersed by the natural permeability of the formation rock. The particular fluid used in this technique is called a fracturing fluid. The fluid raises the pressure until such pressure exceeds the strength of the formation rock. When this occurs, the formation rock fractures and so-called "fractures" begin. As pumping continues, the fractures grow in length, width, and height. The fractures created by the application of this stimulation technique create a conductive path to the hydrocarbon wellbore.

[0041] Ideally, the fracturing fluid should minimize the pressure drop in the wellbore pipes during placement and have sufficient viscosity to carry the proppant material that prevents fracture closure by closing. Further, the fracturing fluid should have a minimal leakage rate to avoid migration of the fluid into the formation rock, especially to create and propagate fractures, and should be decomposed so that no residual substances remain that could potentially prevent the accurate flow of hydrocarbons into the wellbore.

[0042] Some fracturing fluids contain a thickening agent composition comprising: (a) an aqueous medium, and (b) (i) a water-soluble or water-dispersible interpolymer having pendant hydrophobic groups chemically bonded to itself, (ii) a nonionic surfactant having hydrophobic group(s) capable of associating with the hydrophobic groups on said organic polymer, and (iii) a water-soluble electrolyte. Further, the fluid preferably contains a stabilizing amount of thiosulfate. As an example, an interpolymer of acrylamide and dodecyl acrylate was used in combination with a nonionic surfactant (HLB of 10 to 14) to thicken a dilute aqueous solution of KCl and sodium thiosulfate, and the aqueous solution had excellent properties for use as a high-temperature hydraulic fracturing fluid. See, for example, published PCT application WO87 / 01758 pamphlet entitled "Hydraulic Fracturing Method and Composition".

[0043] Some fracturing fluids include an aqueous liquid medium with increased low-shear viscosity obtained by dispersing (1) a water-soluble polymer having pendant hydrophobic groups, such as an acrylamide dodecyl acrylate copolymer, and (2) a water-dispersible surfactant, such as sodium oleate or dodecyl polyethyleneoxy glycol monoether, in an aqueous medium. See, for example, U.S. Patent No. 4,432,881 entitled "Water-Dispersible Hydrophobic Thickening Agent". At least some of the surfactants of the present invention recited herein may be included in these formulations.

[0044] Many flushing fluids contain water, thickeners, polymeric gels, and surfactants. Alternative flushing fluids may contain viscoelastic surfactants instead of polymeric gels.

[0045] 1. Polymeric Gel The polymeric gel can consist of one or more of the following: linear polymers, cross-linked polymers, and / or block copolymers.

[0046] Useful linear polymers include, but are not limited to, guar, derivatives of guar, hydroxyethyl cellulose, derivatives of hydroxyethyl cellulose, and mixtures thereof.

[0047] Useful cross-linked polymers include, but are not limited to, polymers cross-linked with borate ions, zirconate ions, and / or titanate ions.

[0048] Useful block copolymers include, but are not limited to, polyethylene oxide condensates of alkylphenols, such as condensation products of alkylphenols having an alkyl group containing from about 6 to about 20 carbon atoms in a linear or branched configuration and having ethylene oxide, where the ethylene oxide is present in an amount equal to from about 1 to about 10 moles of ethylene oxide per mole of alkylphenol. The alkyl substituents in such compounds can be derived from polymerized propylene, diisobutylene, octane, or nonane.

[0049] 2. Surfactant The pest-killing composition of the present disclosure contains one or more surfactants, also known as surfactant systems. The surfactant system is included for emulsifying the composition and / or for acting as an adjuvant. The surfactant system contains at least one surfactant, which can be an amphoteric surfactant, an ampholytic surfactant, a cationic surfactant, a nonionic surfactant, and optionally contains at least one other surfactant, which can be an amphoteric surfactant, an ampholytic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof. Such surfactants should be physically and chemically compatible with the essential components described herein or should not unduly harm the stability, aesthetics, or performance of the product otherwise.

[0050] Suitable surfactants for use in the flushing liquid of the present disclosure have the formula I:

[0051] [Chemical formula]

[0052] (wherein R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C 1 ~C 6 alkyl, and C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 ~C 12 alkyl, R 4 is C 3 ~C 10 alkyl, the terminal nitrogen may be further substituted with R 5 , R 5 is selected from hydrogen, an oxygen atom, and C 1 ~C 6 alkyl, and C 1 ~C 6The alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counter ion may be associated with the compound. When present, the counter ion may be selected from the group consisting of chloride ion, bromide ion, iodide ion and 4-methylbenzenesulfonate ion), and includes one or more surfactants and / or co-surfactants.

[0053] Suitable surfactants or co-surfactants may include any one or more of surfactants 1 to 7 described herein.

[0054] The concentration of the surfactant system in the flacking fluid formulation may range from about 20 wt.% or more, about 30 wt.% or more, about 40 wt.% or more, or about 50 wt.% or less, about 60 wt.% or less, about 70 wt.% or less or about 80 wt.% or less, based on the weight of the composition, or within any range using these endpoints.

[0055] 3. Thickening agent The flacking fluid formulation may include a water-soluble polymer having a pendant hydrophobic group, such as an acrylamide dodecyl acrylate copolymer.

[0056] 4. Viscoelastic surfactant Viscoelastic surfactants are generally defined as reagents that are substantially polymer-free. Various viscoelastic surfactant fluids are disclosed, for example, in U.S. Patent Nos. 4,615,825, 4,725,372, 4,735,731, Canadian Patent No. 1298697, U.S. Patent Nos. 5,551,516, 5,964,295, 5,979,555 and 6,232,274. One type of well-known polymer-free aqueous fracturing fluid is a viscoelastic surfactant commercialized by the Schlumberger group under the trademark ClearFRAC, as well as a quaternary ammonium salt, N-alkyl-N,N-bis(2-hydroxyethyl)-N-methylammonium chloride and a mixture of isopropanol and brine, preferably brine containing 3 wt% ammonium chloride and 4 wt% potassium chloride.

[0057] 5. Other Additives Optional additives include solids, such as compounds that can reduce or mitigate the effects of sand that can be incorporated into the produced oil. These compounds include clay stabilization or sand stabilization materials. Suitable clay stabilization or sand stabilization materials include epoxy resins, multifunctional cationic polymers. For example, poly(N-acrylamidomethyltriethylammonium chloride) or poly(vinylbenzyltrimethylammonium chloride).

[0058] Still other optional ingredients that can be added to the fluid of the present invention include, but are not limited to, corrosion inhibitors, deoxidizers and bactericides.

[0059] 6. Preparation Method The method includes the step of combining a surfactant or surfactant system, a polymer and / or a viscoelastic surfactant with water. This step may also include the step of adding any of the aforementioned additives. The foregoing components and compounds may be added to one another in any one or more orders, in any amounts, and in one or more separate steps, for example, added in whole or in part. In some methods using the flushing fluid, a significant amount of water is combined with the fluid when injecting into a well.

[0060] 7. Method of Use The flushing fluid formulation of the present disclosure can be in a liquid form at room temperature and atmospheric pressure with important components solubilized therein.

[0061] When a concentrated flushing fluid is produced, it is intended to be mixed with an aqueous medium, and the mixing with the aqueous medium can occur before and / or during the use of the fluid. The concentrated formulation can be added to the tank before, simultaneously with, or after the addition to the tank of the aqueous medium (water). The concentrated fluid can be significantly diluted upon injection into the well, where the well itself already contains water. In some examples, the fluid is injected into the well and the introduction of water, or in some examples additional water, can follow.

[0062] The water content in the diluted flushing formulation of the present disclosure can be about 75 wt.% or more, about 90 wt.% or more, about 99 wt.% or more, or about 99.9 wt.% or more based on the total weight of the diluted composition, and ultimately depends on the amount of water required to dilute the flushing raw material in the concentrated pest control formulation of the present disclosure to the desired concentration as a ready-to-use composition.

[0063] When mixed with and diluted in an aqueous medium, the components of the fluid are intended to be evenly distributed in the aqueous medium.

[0064] III. Formulations for Improved Oil Recovery (IOR) Crude oil and / or naturally occurring gas are present within the pores of certain subterranean rock formations. Typically, the initial or primary recovery of crude oil and / or naturally occurring gas uses the pressure within the oil reservoir to push the crude oil upward through a wellbore. During primary recovery, only a small percentage, typically on the order of 10% to 30% of the crude oil, is extracted at a given location in most oil reservoirs.

[0065] Additional amounts of oil can be produced using water flooding or gas injection, known as secondary recovery. Secondary recovery is relatively inexpensive and is effective for additional production of up to 5% to 20% of the original oil in the reservoir. Secondary recovery applies pressure to the oil reservoir to push the crude oil upward through a wellbore. However, primary and secondary recovery processes can extract less than half of the original oil in the reservoir. Much of the remaining oil is not continuous and is held in the rock by very strong capillary forces. Due to cost, many wells are not used after the primary and secondary recovery processes are completed.

[0066] Additional processes to increase the amount of oil extracted are sometimes referred to as enhanced oil recovery (EOR), or improved oil recovery (IOR), or tertiary recovery. EOR serves to improve oil displacement by reducing the interfacial tension (IFT) between oil and water and also by restoring reservoir pressure to extract crude oil. The three main types of EOR include chemical or caustic flooding, miscible displacement using carbon dioxide (CO 2 ) injection or hydrocarbon injection, and thermal recovery using steam flooding or in-situ combustion.

[0067] Another method for improving oil recovery from wells is the miscible gas process. The miscible gas process is carried out with carbon dioxide and can reduce the viscosity of the crude oil present in the underground formation to increase the flow to hydrocarbon production wells. Carbon dioxide, which acts as a solvent to reduce the viscosity of the crude oil, is an effective and relatively inexpensive miscible gas. During the procedure of the miscible carbon dioxide process, carbon dioxide is typically in the liquid and / or supercritical phase. A method used to increase the effectiveness of the miscible gas process is to add a foaming surfactant to the process.

[0068] Miscible displacement induces miscible gas into the oil reservoir. Carbon dioxide is most commonly used because the gas reduces oil viscosity and is not more expensive than liquefied petroleum gas.

[0069] Thermal recovery induces heat into the oil reservoir to reduce the viscosity of the crude oil, and as a result, the oil flows towards the wellbore. During thermal recovery, the crude oil undergoes physical and chemical changes due to the influence of the supplied heat. Physical properties, such as viscosity, specific gravity, and IFT, are altered. Chemical changes are involved in different reactions, such as cracking and dehydrogenation. However, assembling the huge equipment and piping systems to generate and transport large amounts of CO 2 is costly, and many oil fields are located in places where it is impossible to assemble such equipment. Also, CO 2 is extremely suitable for light oil fields. Thermal recovery is only suitable for certain oil fields, especially those with no depth and where heavy oil gushes out, while for injection, inexpensive fluids such as viscous water, and sometimes followed by water alone, are used. The injection of surfactants, viscous agents, and water is involved in the displacement of the crude oil towards the production well.

[0070] Yet another tertiary recovery process involves chemical or caustic methods. This type of EOR uses a water flood that includes surfactants, polymers, and / or caustic compounds. The water flood reduces IFT and pushes the crude oil out of the rock. This crude oil, which is in a fixed form as droplets trapped in the capillaries, can be made mobile by an injection that is a water flood with surfactants. The surfactant interacts with the crude oil to form microemulsions that reduce the capillary trapping force to a very low level. Once made mobile, the crude oil forms growing oil accumulations such that almost all of the oil does not remain in the flooded portion of the reservoir. After the water flood, the injection may be followed by inexpensive fluids, such as viscous agents, and later by water alone. The injection of surfactants, viscous agents, and water is involved in the displacement of the crude oil to the production wells. Several patents and publications discuss methods for enhanced oil recovery using surfactants.

[0071] The present invention is involved in the use of various amphoteric surfactants including, but not limited to, alkylamidopropyl betaine sulfonate, alkyldimethyl betaine sulfonate, alkylhydroxy sultaine sulfonate, alkyl sulfobetaine sulfonate and alkylamine oxide sulfonate as low adsorption surfactants for uses including, but not limited to, IOR, drilling, viscoelastic surfactants, acid treatment, fracturing, foaming and production. The present invention is involved in the use of a sulfonating agent to react with the double bonds of certain amphoteric surfactants including, but not limited to, alkyleneamidopropyl betaine, alkylene dimethyl betaine, alkylene hydroxy sultaine, alkylene sulfobetaine and alkylene amine oxide to produce the corresponding sulfonated amphoteric surfactants. The sulfonated amphoteric surfactants have been found to provide ultra-low interfacial tension (IFT), viscoelastic properties, compatibility with brines containing large amounts of salts and divalent ions, and low adsorption to reservoir rocks. Some embodiments of the present invention are involved in the use of various amphoteric surfactants including, but not limited to, alkylamidopropyl betaine sulfonate, alkyldimethyl betaine sulfonate, alkylhydroxy sultaine sulfonate, alkyl sulfobetaine sulfonate and alkylamine oxide sulfonate as low adsorption surfactants for uses including, but not limited to, IOR, drilling, viscoelastic surfactants, acid treatment, fracturing, foaming and production.

[0072] 1. Aqueous injection fluid / carrier Aqueous carriers that can be used in various formulations include, but are not limited to, water, brine, river water, synthetic brine and seawater. Brine often contains, for example, one or more salts of monovalent and / or divalent inorganic salts.

[0073] In many of the formulations of the present invention, the carrier is included as about 40 wt.% of the disclosed aqueous hydraulic fracturing composition (e.g., the carrier is present in the composition in an amount ranging from at least about 40 wt.% to about 99.88 wt.%, such as 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.% or more). The carrier can be any suitable material that can dissolve the active ingredients and adjuvants and can deliver the hydraulic fracturing composition to the hydraulic fracturing site. Water is a convenient carrier for the liquid embodiments of the disclosed compositions. The hydraulic fracturing composition can also be prepared as a gel, dip, foam or spray.

[0074] 2. Alkali Alkalis are used as is known in the art in some cases to form "in situ" surfactants that act synergistically with the injected surfactant. Examples of alkalis that can be used to practice the present invention include, but are not limited to, sodium hydroxide, sodium carbonate, sodium borate, sodium silicate. Typically, the alkali is used at a concentration of 0 to about 5 wt.% of the injection fluid, but can be further added as needed.

[0075] 3. Thickening agent Examples of thickening agents that can be used to practice the present invention include, but are not limited to, polyacrylamide, AMPS copolymers, xanthan gum, other natural and synthetic gums, and polymers used to increase the viscosity of the injection fluid when control of mobility and displacement efficiency is required, as are generally known in the art. Generally, thickening agents can be used as needed, but are used at a concentration of 0 to about 1 wt.% of the injection fluid.

[0076] 4. Co-solvent The co-solvent can be used as is known in the art to reduce the viscosity of the injection fluid and improve freeze-thaw or compatibility at high concentrations. Exemplary co-solvents include, but are not limited to, C1-C8 alcohols, C1-C8 alcohol alkoxylates, and glycerin. The co-solvent is used at a concentration of 0 to about 50 wt.% of the injection fluid.

[0077] 5. Surfactants and Co-surfactants Examples of surfactants and co-surfactants that can be used include one or more compounds selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. These are used by those skilled in the art. Generally, the co-surfactant is used at a concentration of 0 to about 5 wt.% of the total injection liquid formulation, but can be added further as needed.

[0078] The IOR fluid formulation of the present invention includes one or more surfactants, also referred to as a surfactant system. The surfactant system can be used as a dispersant or wetting agent. The surfactant system can also be used as an emulsifier component to form a stable emulsion in the form of a liquid fungicide when prepared for agricultural use. The emulsifier component can also be used to form a stable emulsion concentrate. The surfactant system can be at least one surfactant that can be an amphoteric surfactant, zwitterionic surfactant, cationic surfactant, nonionic surfactant, and optionally at least one other surfactant that can be an amphoteric surfactant, zwitterionic surfactant, cationic surfactant, nonionic surfactant, or a combination thereof.

[0079] Suitable surfactants for use in the fungicidal formulations of the present disclosure are of formula I:

[0080]

Chemical formula

[0081] (wherein R 1 and R 2 are hydrogen, an oxygen atom and C1 ~C 6 Independently selected from alkyl, C 1 ~C 6 The alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 ~C 12 alkyl, R 4 is C 3 ~C 10 alkyl, and the terminal nitrogen may be further substituted with R 5 , R 5 is hydrogen, an oxygen atom and C 1 ~C 6 selected from alkyl, C 1 ~C 6 The alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counterion may be associated with the compound. If present, the counterion may be selected from the group consisting of chloride ion, bromide ion, iodide ion and 4-methylbenzenesulfonate ion) one or more surfactants and / or cosurfactants.

[0082] Suitable surfactants or cosurfactants may include any one or more of surfactants 1 to 7 described herein.

[0083] The total amount of one or more surfactants in the fungicidal formulation may be about 1 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, or about 15 wt.% or less, about 20 wt.% or less, about 25 wt.% or less, about 30 wt.% or less, about 35 wt.% or less, or within any range using these endpoints.

[0084] 6. Coemulsifier or cosurfactant Some embodiments of the present invention include at least one surfactant according to the present disclosure, as well as at least one additional surfactant, for example, a sulfosuccinate surfactant, and at least one sulfosuccinate surfactant selected from monoester sulfosuccinate surfactants and diester sulfosuccinate surfactants, and surfactant mixtures of blends thereof, and, in particular, alkanolamides, alkyl sulfates, alpha olefin sulfonates, betaines, fatty acid soaps, aliphatic alcohol alkoxylates, ethoxylated sorbitan esters, and sulfobetaines, further blended with additional surfactants, and, in particular, produce an increased amount of stable foam exhibiting an extended half-life in seawater, seawater / diesel mixtures, and brines. These surfactant mixtures may optionally contain a solvent, which is preferably water, or an aqueous solution containing salts, a foam booster, for example xanthan gum, an oil which may be a hydrocarbon oil or a vegetable oil, and a thickener or a preservative. Compared to prior art foam-forming compositions, these formulations provide improvements in the amount of foam produced, foam stability, and foam duration.

[0085] Some of the commercially desirable foaming surfactant compositions described herein exhibit improved foaming performance in a variety of aqueous media, including seawater (which typically contains about 3.5% dissolved salts by average mass fraction, the majority of which is sodium chloride) and brine (i.e., an aqueous salt solution typically containing up to 12%, e.g., from 0.1% to 11% by mass fraction, of dissolved salts of monovalent and divalent cations). The improved surfactant compositions function at ambient temperature (typically 23 °C), and both lower temperatures, e.g., from 1 °C to 23 °C, or elevated temperatures, e.g., above 23 °C up to 95 °C. This involves steps to create formulations that increase the total volume of the foam and improve foam stability and the longest duration of the foam (i.e., the half-life of the foam, the time required to separate 50% of the volume of the liquid medium from the original foam). Further, the foaming surfactant compositions fully described herein advantageously exhibit improved performance at lower concentrations, thereby reducing exposure to the environment and workers, while at the same time presenting a lower tendency to form oil-in-water emulsions, which is also advantageous as it can simplify oil recovery in production.

[0086] IV. Emulsions and / or Foams Aqueous foaming surfactant compositions can be made from water or an aqueous salt solution, such as seawater or brine, optionally in mixture with a hydrocarbon, or a hydrocarbon, and a mixture of one or more of the foaming surfactant compositions described herein in an effective foaming amount. It is also possible to use a supercritical gas as the liquid medium, to which is added a foaming surfactant composition in an effective foaming amount as described herein. The types of surfactants detailed in the present invention include anionic surfactants, mixtures of two or more anionic surfactants, and any combination thereof with cationic, amphoteric, zwitterionic and nonionic surfactants, and the gas can include, for example, one or more of air, carbon dioxide, nitrogen, methane or other natural and produced gases.

[0087] One way to improve oil recovery from wells is the miscible gas method. The miscible gas method is carried out with carbon dioxide and can reduce the viscosity of the crude oil present in the subterranean formation to increase the flow to the hydrocarbon production well. Carbon dioxide, which acts as a solvent to reduce the viscosity of the crude oil, is an effective and relatively inexpensive miscible gas. During the procedure of the miscible carbon dioxide method, carbon dioxide is typically in the liquid and / or supercritical phase. A method used to increase the effectiveness of the miscible gas method is to add a foaming surfactant to the process.

[0088] In one aspect, the present invention includes a method for recovering oil or natural gas from a reservoir or subterranean oil- or gas-bearing geology during injection of a gas using a foaming surfactant composition according to the present invention. The method contemplated by the present invention includes contacting oil or gas in a formation with either one or more of a foaming surfactant composition and an injected gas to assist in oil recovery. The methods contemplated herein for the recovery of oil or natural gas using the foaming surfactant compositions described herein can be carried out as part of any one or more of the primary, secondary, or tertiary recovery techniques standard in the industry. The foaming surfactant compositions of the present invention can be used as a solution in a solvent or liquid vehicle, and the solvent is selected from water, aqueous salt solutions, liquefied gases, supercritical gases, and mixtures thereof. Typically, the surfactant is incorporated into an aqueous medium and foam is created. When an aqueous salt solution is used as the solvent, an aqueous foaming surfactant composition is obtained, and the combination of the foaming surfactant composition and water or an aqueous salt solution preferably contains dissolved inorganic salts in a mass fraction of at least 0.2% and preferably up to 10%, from which foam can be generated by intimate mixing with gas in a foam generator. The foam can also be generated in situ through introduction into the subterranean oil- or gas-bearing geology, which in many cases also contains water or an aqueous salt solution, of an alternative slug of gas and the foaming surfactant composition under pressure. A dissolved inorganic salt of the same mass fraction of at least 0.2% and preferably up to 10% is thereby typically obtained.

[0089] In the recovery of hydrocarbons, such as oil and natural gas, the role played by emulsions includes, for example, bubbles that can be used to enhance the recovery of gas or oil from a well source. In some embodiments, the emulsion can be formed with oil or gas recovered, for example, from a well or from the products of a bioprocess. In some embodiments, the surfactants of the invention disclosed herein are used to create emulsions, such as bubbles. In yet other embodiments, the surfactant can be used to split an emulsion containing the recovered oil or gas.

[0090] Bubbles can be formed by adding an effective amount of at least one anionic surfactant present in an effective amount of a high-salt foaming fluid composition that produces an IFT of only 10 - mN / m. The anionic surfactant can be the surfactant of the invention, or a sulfonate surfactant and / or a sulfate surfactant. The foaming fluid composition can be used to perform operations including, but not limited to, gas lift operations, drilling operations, completion operations, stimulation operations, fracturing operations, injection operations, enhanced oil recovery operations, and combinations thereof.

[0091] The foaming fluid is used in a variety of applications during the recovery of hydrocarbons from subterranean reservoirs. The foaming fluid includes a base fluid, a foaming agent, and a fluid containing a gas including, but not limited to, nitrogen, carbon dioxide, air, methane, etc. The base fluid can be foamed to reduce the amount of fluid loss to the formation, reduce the amount of base fluid required, and / or enhance the proppant suspension in the fracturing fluid. A "foaming agent" is defined herein as an agent that promotes the foaming of the base fluid when the gas is mixed.

[0092] The foamed fluid can also be used during stimulation operations (such as gas well unloading) to displace any existing fluid and / or formation fluid present in the wellbore. "Existing fluid" is defined herein as the fluid present in the subterranean reservoir wellbore prior to introducing the foaming additive and / or the foamed fluid composition into the subterranean reservoir wellbore. "Formation fluid" is defined herein as any fluid produced from an oil-bearing subterranean formation, including but not limited to oil, natural gas, water, etc. Formation fluid is considered an existing fluid, but the existing fluid may not necessarily be a formation fluid. For example, other fluids in the well can be injected into the subterranean reservoir wellbore and still be present in the wellbore when the foaming additive is introduced into the wellbore. Thus, the fluid in the well (such as drilling fluid, completion fluid, fracturing fluid, injection fluid, etc.) can be the "base fluid" when introducing the foaming additive and gas into the subterranean reservoir wellbore.

[0093] The base fluid of the foamed fluid can be drilling fluid, completion fluid, stimulation fluid, fracturing fluid, injection fluid, and combinations thereof. Non-limiting examples of the use of such fluids can be involved in, for example, oil or gas well unloading, enhanced oil recovery operations, heavy oil recovery, drilling operations, fracturing operations, pressure pumping, cementing, acid treatment, or other stimulation operations.

[0094] Non-limiting examples of foamed drilling fluids can be those when the drilling operation requires a drilling fluid with a low density. For example, the density of the foamed drilling fluid can independently range from about 2.0 ppg (about 0.24 g / cm 3 ) to about 8.0 ppg (about 0.96 g / cm 3 ).

[0095] Drilling fluids are typically classified according to their base fluid. In water-based fluids, the solid particles are suspended in a continuous phase consisting of water or brine. Oil can be emulsified in water, which is the continuous phase. "Water-based fluid" is used herein to include fluids having an aqueous continuous phase, which can be all water or brine, oil-in-water emulsion, or oil-in-brine emulsion. Brine-based fluids are, of course, water-based fluids where the aqueous component is water-based. Oil-based fluids are the opposite or reverse of water-based fluids.

[0096] "Oil-based fluid" is used herein to include fluids having a non-aqueous continuous phase, which can be all oils, non-aqueous fluids, water-in-oil emulsions, water-in-nonaqueous solution emulsions, brine-in-oil emulsions or brine-in-nonaqueous solution emulsions. In oil-based fluids, the solid particles are suspended in a continuous phase consisting of oil or another non-aqueous fluid. Water or brine can be emulsified in oil, and thus oil is the continuous phase. In oil-based fluids, the oil can consist of, but is not limited to, any oil or water-immiscible fluid including diesel, mineral oil, esters, refinery cuts and blends or alpha olefins. The oil-based fluids as defined herein can also include synthetic base fluids or synthetic-based muds (SBM) which are more synthetically produced rather than refined from naturally occurring materials. Synthetic base fluids often include, but are not necessarily limited to, olefin oligomers of ethylene, esters made from vegetable fatty acids and alcohols, ethers and polyethers made from alcohols and polyalcohols, paraffinic or aromatic hydrocarbon alkylbenzenes, terpenes and other natural products, as well as mixtures of these types of brines.

[0097] One type of drilling operation involves cementing where cement is pumped into the wellbore. Cementing operations can be used to seal the annulus after the casing string has passed through, to seal a lost circulation zone, to set a plug in an existing well and then push it out with directional tools, or to pack the well with a plug so that it can be abandoned. Before starting the cementing operation, the volume of cement to be placed in the wellbore, as well as the physical properties of the required slurry and set cement, including density and viscosity, are determined. The drilling fluid can be displaced to place cement in the wellbore. When performing primary cementing and repair cementing operations in the wellbore, the cement slurry used often has to be lightweight to prevent excessive hydrostatic pressure generated in the subterranean formations penetrated by the wellbore. As a result, a variety of lightweight cement slurries, including foamed cement slurries, have been developed and used.

[0098] In addition to being lightweight, foamed cement slurries contain compressed gas and improve the slurry's ability to maintain pressure and prevent the flow of formation fluid into and through the slurry during its transition time, i.e., the time during which the cement slurry changes from a complete fluid to a solid mass. Other surfactants can be used as foam stabilizers to prevent premature separation of the foam slurry into slurry and gas components, in addition to being used as foaming agents, and can also be added to the slurry. Foamed cement slurries can have the property of low fluid loss.

[0099] The expected functions and properties of the completion fluid vary widely. The completion fluid may be placed in the well to facilitate final operations prior to the start of production. The completion fluid is typically a brine containing chlorides, bromides, formates, but may be any harmless fluid having appropriate density and flow characteristics. Suitable salts for forming brines include, but are not necessarily limited to, sodium chloride, calcium chloride, zinc chloride, potassium chloride, potassium bromide, sodium bromide, calcium bromide, zinc bromide, sodium formate, potassium formate, ammonium formate, cesium formate, and mixtures thereof. The chemical compatibility of the completion fluid with the reservoir formation and fluid can be extremely important. Chemical additives, such as polymers and surfactants, are known in the art to be introduced into brines used in well servicing fluids for various reasons including, but not limited to, increasing viscosity and increasing the density of the brine.

[0100] Service fluids, such as workover fluids, stimulation fluids, and remedial fluids, have several functions and properties necessary for the repair of damaged wells. Such fluids can be used for the separation of pre-formed emulsions and for the removal of formation damage that may have occurred during drilling, completion, and / or production operations. The terms "workover operation" and "workover" are defined herein to include the reduction of the viscosity of damaged gels and / or the partial or complete removal of any type of damage from subterranean formations. Similarly, the term "workover fluid" is defined herein to include any fluid that can be useful in a workover operation. A stimulation fluid can be a treatment fluid, such as, by way of non-limiting example, a fracturing fluid and / or a matrix stimulation fluid, prepared to stimulate, restore, or enhance the productivity of a well.

[0101] Hydraulic fracturing is a type of stimulation operation that uses pumping rates and hydraulic pressures to fracture or create cracks in subterranean formations in a process to improve hydrocarbon recovery from the formations. When cracks are created, proppants with high permeability compared to the formation permeability are pumped into the fractures to support the opening of the cracks. If the applied pumping rates and pressures are reduced or removed from the formation, the high permeability proppants hold the crack openings, and the cracks or fractures cannot fully close or heal. The supported cracks or fractures result in high permeability paths that increase the wellbore formation area and lead to enhanced hydrocarbon production.

[0102] Another type of stimulation operation is where oil or gas wells are "unloaded". In most gas wells, water and / or condensate are produced along with the gas. In mature gas wells, as the formation pressure and gas flow rate gradually decline, the well becomes "unloaded" with liquid. Since the treatment of wells loaded with liquids having higher condensate cuts is problematic, operators use various methods to prevent liquid loading in marginal gas wells.

[0103] The unloading of oil or gas wells can be essential when primary production techniques (i.e., using only the initial formation energy to recover crude oil) followed by secondary techniques such as water flooding recover only a small percentage of the original reserves present in the formation. The average recovery rate is approximately 25 to 35% in oil fields and approximately 70% in gas fields after secondary recovery operations. Gas well production systems and oil well production systems are generally limited in production due to the loading of oil and water in the flowline.

[0104] Gas lift and / or deliquification of wells can enable wells with liquid loading problems to return to a continuous flow state, enhance the flow of current production wells, reopen wells, and combinations thereof. Typically, since oil and / or gas are produced from reservoir formations, the pressure in the reservoir formations decreases and production declines. Further, due to completion problems, well production may decline over a long period of time and it may be difficult to reopen the wells. A commonly used method for deliquifying or "unloading" these wells is through the application of chemical foaming agents.

[0105] The use of in situ generated foam by injection of surfactant-altered gas (SAG) is described as an alternative to polymers operating in alkaline / surfactant / polymer (ASP) enhanced oil recovery (EOR) processes in R.F. Li et al., "Foam Mobility Control for Surfactant Enhanced Oil Recovery", SPE 113910, SPE / DOE Symposium on 20 Improved Oil Recovery, Tulsa, Okla., SPE Journal, March 2010.

[0106] Micellar alkaline soap substances, etc., can be used to reduce the interfacial tension between oil and water in the reservoir and impart mobility to the oil present in the reservoir, while polymers, such as polyacrylamide or polysaccharide, can be used to improve the displacement efficiency, which is a measure of the effectiveness of an EOR operation that depends on the mobility ratio and the volume of the reservoir contacted by the injected fluid.

[0107] In a non-limiting alternative embodiment of the method, the method may include unloading an oil or gas well in a subterranean oil-bearing formation by introducing a foamed fluid composition into a subterranean reservoir well having an existing fluid therein. The foamed fluid composition may have, or may include, a base fluid, a gas, at least one anionic surfactant, and at least one second surfactant selected from the group consisting of cationic surfactants, nonionic surfactants, zwitterionic surfactants, and combinations thereof. The at least one anionic surfactant is selected from the group consisting of sulfonate surfactants and / or sulfate surfactants, and the anionic surfactant includes a C20-C24 carbon chain and an internal olefin. The foamed fluid composition has a salinity of 30,000 TDS or more. The surfactant is present in an effective amount to foam the composition. The method further includes the step of at least partially replacing the existing fluid in the subterranean reservoir well.

[0108] Another form of foamed fluid composition is further provided having a base fluid, a gas, at least one anionic surfactant, and at least one second surfactant. The base fluid can be, or can include, an oil-based fluid, an aqueous-based fluid, and combinations thereof. The anionic surfactant has a hydrophobic chain of at least 20 carbon atoms, and the anionic surfactant is a sulfonate surfactant, a sulfate surfactant, or a combination thereof. The anionic surfactant is present in the foamed fluid composition in an effective amount to obtain an IFT of from about 10-1 mN / m to about 10-3 mN / m. The at least one second surfactant includes, but is not necessarily limited to, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and combinations thereof. The foamed fluid composition has a salinity of 30,000 total dissolved solids (TDS) or more.

[0109] In another non-limiting embodiment of the foamed fluid composition, the anionic sulfonate surfactant(s) is C 20 ~C 24It may have or contain a carbon chain and internal olefins therein, and the amount of at least one anionic surfactant ranges from about 1 vol% to about 50 vol% based on the total foaming fluid composition.

[0110] In one form, a method is provided that may include the step of working with a foaming fluid composition. The foaming fluid composition may have or contain a base fluid, a gas, and at least one anionic surfactant having a hydrophobic chain of at least 20 carbon atoms, and the anionic surfactant is selected from the group consisting of sulfonates. 1. Surfactant Suitable surfactants for use in the herbicide formulations of the present disclosure are of formula I:

[0111] [Chemical formula]

[0112] (wherein R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C 1 ~C 6 alkyl, and C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 ~C 12 alkyl, R 4 is C 3 ~C 10 alkyl, the terminal nitrogen may be further substituted with R 5 , and R 5 is selected from hydrogen, an oxygen atom, and C 1 ~C 6 alkyl, and C 1 ~C 6The alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counter ion may be associated with the compound. When present, the counter ion may be selected from the group consisting of chloride ion, bromide ion, iodide ion and 4-methylbenzenesulfonate ion), and includes one or more surfactants and / or co-surfactants.

[0113] Specifically, suitable surfactants or co-surfactants may include any one or more of surfactants 1 to 7 described herein.

[0114] 2. Second surfactant At least one anionic surfactant has a hydrophobic chain of 12 to 24 carbon atoms, the anionic surfactant is selected from the group consisting of sulfonate surfactants, sulfate surfactants, and combinations thereof, and at least one second surfactant is selected from the group consisting of cationic surfactants, nonionic surfactants, zwitterionic surfactants, and combinations thereof.

[0115] 3. Base fluid The base fluid can be an oil-based fluid or a water-based fluid selected from the group consisting of drilling fluids, finishing fluids, stimulation fluids, fracturing fluids, gas well dewaxing fluids, coiled tubing work fluids, recycled drilling fluids, supply fluids, well cleanout fluids, well intervention fluids, capillary coiled tubing fluids and combinations thereof.

[0116] 4. Gas Any suitable gas known in the art can be miscible with any appropriate liquid portion of the liquid formulation. Such gases include, but are not limited to, air, nitrogen, carbon dioxide, natural gas and any combination thereof.

[0117] V. Fluid for recovering bio-oil Bio-based oils, including edible oils from naturally occurring sources, are essential for human nutrition and, until relatively recently, were also a source of light and even energy. Naturally occurring sources of oil include seeds and fruits, some of which are cultivated primarily as sources of oil. Sources of bio-based oils that can be used in fuels, including biodiesel fuel, include naturally occurring soybeans and bioengineered algae. Any formulation and / or process that can be used to increase recovery and / or improve the quality of the recovered oil is beneficial.

[0118] Other sources of bio-based oils include distillation waste liquors from the fermentation of raw materials such as corn, as well as from the processing of oil-rich plants such as soybeans and algae. Some embodiments of the present invention include formulations for assisting in the extraction of emulsified oil from an emulsion of oil and water. The composition can include a nonionic surfactant selected from alkoxylated vegetable oils, alkoxylated vegetable fats, alkoxylated animal oils, alkoxylated animal fats, alkyl polyglucosides, alkoxylated glycerols, and mixtures thereof. The composition can include silicon-containing particles. Some methods for recovering oil from the corn ethanol process are also provided. These methods can include the step of adding the composition to a process stream of the corn ethanol process and the step of extracting the oil from the process stream.

[0119] Formulations for recovering edible oils include only reagents characterized as generally recognized as safe (GRAS) by regulatory authorities such as the United States Department of Agriculture and the United States Food and Drug Administration.

[0120] Sources of bio-based oils that can be used in fuels, including biodiesel fuel, include naturally occurring soybeans and bioengineered algae.

[0121] (New paragraph or part of the foregoing?) Most commercial corn oil is produced by the front-end fraction of corn germ during the wet milling process of corn. Recently, a new source of corn oil has been shown as a by-product of the dry milling process used in the ethanol industry. Dry milling is a process that requires less energy and capital investment than wet milling. The corn oil captured in the post-treatment of the dry milling process is not suitable for food use but can be used as a raw material for biodiesel.

[0122] 1. Aqueous component The aqueous component may include, for example, pure water and seawater. Most commonly, the aqueous phase includes water containing one or more inorganic salts.

[0123] 2. Supercritical gas The foam of some inventions contains a supercritical gas, such as carbon dioxide. Supercritical carbon dioxide (CO 2 ) is a fluid state of a gas in which the gas is held at or above the critical temperature and critical pressure. The gas in this state exhibits some properties that are intermediate between those of a gas and a liquid. Supercritical carbon dioxide exists at a temperature of about 31.1 °C or higher and a pressure exceeding about 7.39 MPa.

[0124] 3. Surfactant Suitable surfactants for use in the herbicide formulations of the present disclosure are of formula I:

[0125]

Chemical formula

[0126] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C 1 to C 6 alkyl, and C 1 to C 6The alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 ~C 12 alkyl, and R 4 is C 3 ~C 10 alkyl, and the terminal nitrogen may be further substituted with R 5 , and R 5 is selected from hydrogen, an oxygen atom and C 1 ~C 6 alkyl, and C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counterion may be associated with the compound. When present, the counterion may be selected from the group consisting of chloride ion, bromide ion, iodide ion and 4-methylbenzenesulfonate ion), and includes one or more surfactants and / or cosurfactants.

[0127] Specifically, suitable surfactants or cosurfactants may include any one or more of Surfactants 1 to 7 described herein.

[0128] The aforementioned surfactants are, for example, of the formula: R-NX-CO-CHY 1 -CHY 2 - CO-O-M 4+ (wherein Y 1 is H, Y 2 is (SO 3 M 3+ ), or Y -1 is (SO 3 M 3+ ), and Y 2 is H), and can be combined with other surfactants including sulfosuccinate-type surfaces. M 3+ and M 4+is a cation, which may be the same or different, and is selected from Groups 1 and 2 of the periodic table consisting of alkali metals and alkaline earth metals, preferably Li + , Na + , K + , and also selected from ammonium NH 4+ . R is a straight-chain, branched, or cyclic aliphatic radical having 8 to 24 carbon atoms and optionally one or more carbon-carbon double bonds, or a mixture of two or more such radicals. X can be a hydrogen atom or an alkyl carboxylate group -(CRR)-COOM 2+ . R' and R can both be H, or R can be H and also R can be -CH COOM 3+ . M 3+ and M + are cations, which may be the same or different, and are also selected from Groups 1 and 2 of the periodic table consisting of alkali metals and alkaline earth metals, preferably Li, Na + , K + , and also from ammonium NH. Particularly preferred alkali metal ions for M 3+ , M + , M 2+ and M 4+ are, independently of each other, the sodium cation Na + , and the potassium cation K + .

[0129] Any other surfactant optionally included in the indicated separation aid composition can be, for example, a nonionic surfactant, a cationic surfactant or an anionic surfactant. The surfactant(s) can be nonionic surfactants such as, for example, ethoxylated castor oil, ethoxylated sorbitan esters, PEG, poloxamers, acetylene glycols or sulfonates, or combinations thereof. Nonionic surfactants can be, for example, nonionic polyethylene glycols such as ethoxylates of carboxylic acids, ethoxylates of mono-, di- or triglycerides, ethoxylates of mono-, di- or triesters of sorbitan, or ethoxylates of aliphatic alcohols. Ethoxylated sorbitan esters are commercially available as TWEEN or polysorbate series surfactants. Other suitable nonionic surfactants are mono-, di- or triglycerides based on fatty acids having 12 to 22 carbon atoms, or mono-, di- or triesters of sorbitan based on fatty acids having 12 to 22 carbon atoms. Commercial sources of nonionic surfactants that can be used in the separation aid of the present invention include, for example, Lumisorb Polysorbates from Lambent Technologies Corporation (Gurnee, Ill., USA). The nonionic surfactant can be at least one poloxamer. A poloxamer can be a nonionic triblock copolymer that includes a central block of a hydrophobic polyalkylene oxide block with hydrophilic polyalkylene oxide blocks adjacent on both sides thereof. Poloxamers are commercially available food grade products. Commercial sources of poloxamers are, for example, PLURONIC® copolymers from BASF Corporation (Florham Park, N.J., U.S.A.).

[0130] The water solubility of surfactants, such as nonionic surfactants, can be related to the hydrophilic-lipophilic balance (HLB) value or number. Nonionic surfactants can have an HLB value of at least about 6, or at least about 9, or at least about 12, or from about 6 to 20, or from about 7 to about 19, or from about 8 to about 18, or from about 9 to about 17, or from about 10 to about 16, or other values. The water solubility of nonionic surfactants can be related to the hydrophilic-lipophilic balance (HLB) value or number. The HLB value can be calculated by conventional means. For example, the HLB value of a nonionic surfactant can be calculated by dividing the molecular weight percentage of the hydrophilic portion of the nonionic surfactant by 5. For example, a nonionic surfactant containing 80 moles of 96 hydrophilic portions (total) can have an HLB value calculated to be 16 (i.e., 80 / 5 = 16). HLB values above 20 are relative or comparative values.

[0131] Formulations of some inventions can include one or more surfactants in an amount of about 0 wt.% or more, about 2 wt.% or more, about 4 wt.% or more, about 6 wt.% or more, about 8 wt.% or more, or about 10 wt.% or less, about 12 wt.% or less, about 14 wt.% or less, about 16 wt.% or less, or within any range using these endpoints.

[0132] 4. Oil Oils that can be used to practice the present invention include alkoxylated vegetable oils selected from the group consisting of ethoxylated castor oil, ethoxylated soybean oil, ethoxylated palm kernel oil, ethoxylated almond oil, ethoxylated corn oil, ethoxylated canola oil, ethoxylated rapeseed oil, and ethoxylated coconut oil.

[0133] The oil contained in the indicated separation aid can be, for example, mineral oil, triglyceride vegetable oil, hydrocarbon oil or any combination thereof. The mineral oil can be, for example, white mineral oil or mineral seal oil. Examples of mineral oil can be atmospheric residue, vacuum gas oil obtained by distillation of crude oil, and vacuum residue obtained by vacuum distillation of atmospheric residue, their hydrotreated oils, pyrolysis oils and / or mixtures thereof. Among these mineral oils, atmospheric residue, vacuum residue and their hydrogenated products or pyrolysis products are referred to as residue oils in the present invention. The triglyceride vegetable oil can be, for example, triglyceride corn oil. The hydrocarbon oil can be, for example, white mineral oil or any combination thereof. Commercial sources of oil that can be used in the separation aid of the present invention include, for example, Clarion White Mineral Oil 70, CITGO Petroleum (Houston, USA).

[0134] 5. Lecithin The lecithin used as a separation aid can be of natural origin, modified origin or synthetic. The lecithin that can be used in the present invention can be lecithin derived from any plant, animal or microbial source. Suitable lecithin starting materials are commercially available and include available soybean lecithin and egg yolk lecithin products. Lecithin is obtained from natural sources such as egg yolk and plants such as soybeans, maize, rapeseed, etc., which are by-products of the refining of vegetable oils. Soybean oil is the largest source of commercial lecithin. The composition of commercial lecithin depends on the source, the method of preparation and the degree of purification, but in its purest form it consists mainly of phosphatides. Commercial lecithin is, for example, a co-product of oil processing obtained during the refining step. For example, soybean lecithin is a complex mixture containing phospholipids and triglycerides and accompanied by other components in small amounts such as plant glycolipids, plant sterols, tocopherols and fatty acids. The main phospholipids present in plant lecithin are phosphatidylcholine, phosphatidylethanolamine and phosphatidylinositol. Egg yolk lecithin of eggs contains phosphatidylcholine and phosphatidylethanolamine as the main phospholipids. Lecithin can be extracted chemically (using hexane) or mechanically from easily available sources such as soybeans. Lecithin has low solubility in water. In aqueous solution, its phospholipids can form liposomes, bimolecular membrane sheets, micelles or lamellar structures depending on hydration and temperature. This results in a type of material that is usually classified as amphiphilic. As used herein, "modified lecithin" refers to, but is not limited to, acetylation, hydroxylation, hydrogenation, hydrolysis products, chlorination, bromination, iodination, halogenation, phosphorylation reactions and sulfonation of lecithin, as well as any other modification known to those skilled in the art. Acetylated lecithin can be produced, for example, using carboxylic acid anhydrides such as acetic anhydride for the acetylation of phospholipids from plant lecithin, as shown in, for example, U.S. Patent No. 3,301,881, which is incorporated herein by reference in its entirety.The enzyme process can be used for the preparation of acetylated lipids from plant lecithins, such as soybean lecithin, rapeseed lecithin, and animal lecithins such as egg yolk lecithin, or pure phosphatidylethanolamine isolated from the above lecithins. Commercial lecithins can be acetylated, for example, in the presence of lipase from Mucor miehei having 1,3 - specificity, as shown in U.S. Patent No. 6,403,344, which is hereby incorporated by reference in its entirety, using vinyl acetate as an acylating agent. In acetylated lecithin, for example, acetylation mainly occurs at the amino group of phosphatidylethanolamine. The scale of acetylation in modified lecithin can be partial or complete when used. The scale of acetylation in modified lecithin can be, for example, from about 5% to 100%, or from about 10% to about 99%, or from about 15% to about 95%, or from about 20% to about 90%, or from about 25% to about 75%, or other values. Lecithin further contains several chemical functional groups that make it susceptible to various chemical reactions. These groups include carbon - carbon double bonds, esters, phosphonate esters, amines, and hydroxyl groups. Modification can also result in transesterified lecithin. Further, lecithin can be a modified enzyme. As used herein, "phosphatide" (phospholipid) refers to, but is not limited to, a mixture of phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, phosphatidic acid, N - acyl phosphatidylethanolamine, and other related minor components. Commercial sources of lecithin or modified lecithin that can be used in the separation aid of the present invention include, for example, Solec HR2B from Solae LLC (Memphis, Tenn., USA).

[0135] 6. Silica For example, the separation aid may contain silica, such as fumed silica. The fumed silica can be hydrophobic or hydrophilic. Fumed silica is food grade and may be more desirable for this reason. Condensed fumed silica can be contained in the separation aid, for example, in an amount from about 1 wt% to 10 wt%.

[0136] 7. Water-insoluble solvents and oils Suitable water-insoluble immiscible organic solvents include those derived from or made from natural non-petroleum sources, such as plants and animals, and also include vegetable oils, seed oils, animal oils, etc., such as N,N-dimethylcaprylamide (N,N-dimethyloctanamide), N,N-dimethylcapramide (N,N-dimethyldecaneamide) and mixtures thereof, which are commercially available as Agnique® AMD 810 and Agnique® AMD 10 from BASF Corp. (Florham Park, N.J.), Genegen® 4166, Genegen® 4231 and Genegen® 4296 from Clariant (Charlotte, N.C.), Hallcomid M-8-10 and Hallcomid M-10 from Stepan (Northfield, Ill.), and Amid DM10 and DM810 from AkzoNobel (Chicago, Ill.). Further examples of naturally derived organic solvents include morpholine amide of caprylic / capric fatty acid (C8 / C10), commercially available as JEFFSOL® AG-1730 solvent from Huntsman International LLC (The Woodlands, Tex.).

[0137] Other suitable water-insoluble solvents include aromatic hydrocarbons, mixed naphthalene and alkylnaphthalene fractions, aromatic solvents, especially alkyl-substituted benzenes such as xylene or propylbenzene fractions; C1-C6 esters of fatty acids derived from vegetable, seed or animal oils, such as methyl caproate, methyl caprylate, methyl caprate, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, etc.; ketones such as isophorone and trimethylcyclohexanone (dihydroisophorone); acetate esters such as methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl acetate; and JEFFSOL® alkylene carbonates from Huntsman (The Woodlands, Tex.), cyclic alkyl carbonates also available as dibutyl carbonate from Huntsman, such as propylene carbonate and butylene carbonate, and mixtures of any of the water-immiscible organic solvents described herein may be included.

[0138] The water-insoluble solvent may be present in the herbicidal formulation in an amount of about 0 wt.% or more, about 10 wt.% or more, about 20 wt.% or more, or about 30 wt.% or less, about 40 wt.% or less, about 50 wt.% or less, or within any range using these endpoints.

[0139] 8. Water Water is present in the formulations of the present disclosure and can serve as both an aqueous solvent and a carrier for the ingredients in the described compositions. Some formulations of the present disclosure may contain water in an amount of about 200 g / L or more, about 300 g / L or more, about 400 g / L or more, or about 500 g / L or less, about 600 g / L or less, about 700 g / L or less, about 800 g / L or less, or within any range using these endpoints.

[0140] 9. Other Additives The weeding complex may contain one or more additional compatible raw materials. These additional raw materials may include, for example, one or more pesticides or other raw materials, which may be dissolved or dispersed in the composition and may be selected from acaricides, algicides, feeding inhibitors, avicides, bactericides, bird repellents, and sterilants. Also, any other additional raw materials with functional practicality, such as defoamers, antimicrobial agents, buffers, corrosion inhibitors, dispersants, pigments, fragrances, freezing point depressants, neutralizing agents, odorants, penetration aids, sequestering agents, stabilizers, fixing agents, viscosity modifying additives, water-soluble solvents, etc., may be included in these compositions.

[0141] When the formulation is used in combination with additional active ingredients, for example, the compositions described herein may be formulated with other active ingredient(s) as a premix concentrate and may be tank-mixed with other active ingredients in water.

[0142] 10. Preparation Method The formulations of the present disclosure can be prepared by: 1) the step of preparing a solution in an organic solvent and a surfactant; 2) the step of adding the solution prepared in step 1) to a concentrated solution of a water-soluble salt while thoroughly mixing to form a clear solution; and 3) optionally, the step of adding any additional compatible active or inactive ingredients.

[0143] Alternatively, the formulations of the present disclosure can be prepared by: 1) the step of preparing oil and optionally mixing it with an organic solvent and a surfactant, 2) the step of adding the composition prepared in step 1) to a concentrated solution of a water-soluble salt while thoroughly mixing to form a clear solution; and 3) optionally, the step of adding any additional compatible active or inactive ingredients.

[0144] Suitable water-compatible raw materials that can be added to the formulation include, but are not limited to, water-soluble or water-insoluble dispersing surfactants, such as the surfactants of the present disclosure, water-insoluble active ingredients, and optionally, other inactive ingredients, such as pH buffers, wetting agents, antifreeze agents, defoamers, and biocides.

[0145] 11. Method of Use The solution can be added to a natural source of oil, such as soybean mash or algal biomass, or to a synthetic source of oil, such as the distillation waste liquor from a corn ethanol production process. When mixed with a bio-oil source, the solution can be separated from the oil source by any means known in the art, including, for example, sedimentation, heating, cooling, freezing, etc.

[0146] VI. Surfactant The present disclosure provides a surfactant for use in agricultural products in the form of derivatives of amino acids. The amino acids can be naturally occurring or synthetic, or they can be obtained from the ring-opening reaction of lactams, such as caprolactam. The compounds of the present disclosure have been shown to have surface-active properties and can be used, for example, as surfactants and wetting agents. Specifically, the present disclosure relates to Formula I:

[0147] [Chemical Formula]

[0148] (wherein R 1 and R 2 are independently selected from hydrogen, oxygen atoms, and C 1 -C 6 alkyl, and C 1 -C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 -C 12 alkyl, R 4 is C 3 -C 10 alkyl, the terminal nitrogen may be further substituted with R 5 , and R 5 is selected from hydrogen, oxygen atoms, and C 1 -C 6 alkyl, and C 1 -C 6The alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counter ion may be associated with the compound. When present, the counter ion may be selected from the group consisting of chloride ion, bromide ion, iodide ion and 4-methylbenzenesulfonate ion), providing a compound.

[0149] Certain specific compounds (surfactant 1) obtained according to the present disclosure have the following formula:

[0150]

Chemical formula

[0151] It is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula.

[0152] The second specific compound (surfactant 2) obtained according to the present disclosure has the following formula:

[0153]

Chemical formula

[0154] It is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula.

[0155] The third specific compound (surfactant 3) obtained according to the present disclosure has the following formula:

[0156]

Chemical formula

[0157] It is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula.

[0158] The fourth specific compound (surfactant 4) obtained according to the present disclosure has the following formula:

[0159]

Chemical formula

[0160] It is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate.

[0161] The fifth specific compound (surfactant 5) obtained according to the present disclosure has the following formula:

[0162]

Chemical formula

[0163] It is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide.

[0164] The sixth specific compound (surfactant 6) obtained according to the present disclosure has the following formula:

[0165]

Chemical formula

[0166] It is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride.

[0167] The seventh specific compound (surfactant 7) obtained according to the present disclosure has the following formula:

[0168]

Chemical formula

[0169] It is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate.

[0170] These surfactants can be synthesized by various methods. Such a method includes the step of opening a lactam to obtain an amino acid having an N-terminus and a C-terminus. The N-terminus can be reacted with one or more alkylating agents and / or acids to obtain a quaternary ammonium salt. Alternatively, the N-terminus can be reacted with an oxidizing agent to obtain an amine N-oxide. The C-terminus can be reacted with an alcohol in the presence of an acid to obtain an ester.

[0171] The amino acid can be naturally occurring, or can be synthesized, or can be derived from the ring-opening reaction of a lactam, such as caprolactam. The ring-opening reaction can be an acid or alkali-catalyzed reaction, and an example of an acid-catalyzed reaction is shown below in Scheme 1.

[0172]

Chemical formula

[0173] The amino acid can have as few as 1 or as many as 12 carbons between the N- and C-termini. The alkyl chain can be branched or straight-chain. The alkyl chain can be interrupted by nitrogen, oxygen, or sulfur. The alkyl chain can be further substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen can be acylated or alkylated with one or more alkyl groups. For example, the amino acid can be 6-(dimethylamino)hexanoic acid or 6-aminohexanoic acid.

[0174] Surfactant 1 can be synthesized as shown below in Scheme 2. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is alkylated with methyl iodide in the presence of sodium carbonate.

[0175]

Chemical formula

[0176] Surfactant 2 can be synthesized as shown below in Scheme 3. As shown, the C-terminus of 6-(dimethylamino)hexanoic acid is treated with 2-butyloctanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to obtain the corresponding ester, 2-butyloctyl 6-(dimethylamino)hexanoate as the 4-methylbenzenesulfonate salt.

[0177]

Chemical formula

[0178] Surfactant 3 can be synthesized as shown below in Scheme 4. As shown, 2-butyloctyl 6-(dimethylamino)hexanoate is treated with 1 equivalent of hydrochloric acid to obtain 2-butyloctyl 6-(dimethylamino)hexanoate as the chloride salt.

[0179]

Chemical formula

[0180] Surfactant 4 can be synthesized as shown below in Scheme 5. As shown, the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is treated with 1,4-butanesultone in the reflux of ethyl acetate to obtain the desired sulfonate.

[0181]

Chemical formula

[0182] Surfactant 5 can be synthesized as shown below in Scheme 6. As shown, the N-terminus of the N-terminus of 2-butyloctyl 6-(dimethylamino)hexanoate is treated with hydrogen peroxide in water to obtain the desired N-oxide.

[0183] [Chemical formula]

[0184] Surfactant 6 can be synthesized as shown below in Scheme 7. As shown, the N-terminus of 2-butyl octyl 6-aminohexanoate is treated with 1 equivalent of hydrochloric acid to obtain the corresponding chloride salt.

[0185] [Chemical formula]

[0186] Surfactant 7 can be synthesized as shown below in Scheme 8. As shown, 6-aminohexanoic acid is treated with 2-butyloctanol and p-toluenesulfonic acid (PTSA) in benzene to obtain the corresponding 4-methylbenzenesulfonate.

[0187] [Chemical formula]

[0188] The compounds of the present disclosure demonstrate surface-active properties. These properties can be measured and described in various ways. One way in which surfactants can be described is by the critical micelle concentration (CMC) of the molecule. The CMC is the concentration of surfactant at which micelles form and can be defined as the concentration at which all of the additional surfactants described above are incorporated into the micelles.

[0189] As the surfactant concentration increases, the surface tension decreases. When the surface is completely covered with surfactant molecules, micelles begin to form. This point represents the CMC, as well as the minimum surface tension. Further addition of surfactant does not further affect the surface tension. The CMC can thus be measured by observing the change in surface tension as a function of surfactant concentration. One such method for measuring this value is the Wilhelmy plate method. The Wilhelmy plate is typically a thin iridium-platinum plate attached to a balance by a wire and placed perpendicular to the air-liquid interface. The balance is used to measure the force exerted on the plate by wetting. This value is then used to calculate the surface tension (γ) according to Equation 1: Equation 1: γ = F / l cosθ (where l is equal to the wetting length (2w + 2d, where w and d are the thickness and width of the plate respectively), and the contact angle cosθ between the liquid and the plate is assumed to be 0 if no existing literature value is available) is used to calculate the surface tension (γ).

[0190] Another parameter used to evaluate the performance of surfactants is the dynamic surface tension. The dynamic surface tension is the value of the surface tension for a specific surface or interface lifetime. In the case of a liquid to which a surfactant is added, this can be different from the equilibrium value. Immediately after the surface is created, the surface tension is equal to that of the pure liquid. As described above, since the surfactant lowers the surface tension, the surface tension drops until it reaches the equilibrium value. The time required to reach equilibrium depends on the diffusion rate and adsorption rate of the surfactant.

[0191] One method by which the dynamic surface tension is measured relies on a bubble pressure tensiometer. This device measures the maximum internal pressure of bubbles formed in a liquid by a capillary. The measured value corresponds to the surface tension at a certain surface elapsed time, which is the time from the start of bubble formation to the occurrence of the maximum pressure. The dependence of the surface tension on the surface elapsed time can be measured by the variation in the rate at which the bubbles are generated.

[0192] Surfactant compounds can also be evaluated by their wetting ability on solid substrates, as measured by the contact angle. When a droplet contacts a solid surface under a third medium, such as air, a triple phase line occurs among the liquid, gas, and solid. The angle between the unit vector, which acts at the triple phase line and is the surface tension tangent in the droplet, and the surface is described as the contact angle. The contact angle (also known as the wetting angle) is a measure of the wetting degree of a solid by a liquid. In the case of complete wetting, the liquid spreads completely on the solid and the contact angle is 0°. Wettability is typically measured at a concentration of 1 - 10×CMC for a given compound, but since it is not a concentration-dependent property, wettability measurements can be made at higher or lower concentrations.

[0193] In one method, an optical contact angle goniometer can be used to measure the contact angle. This device extracts the contact angle by analyzing the contour shape of a stationary droplet on the surface using a digital camera and software.

[0194] Potential uses for the surfactant compounds of the present disclosure include formulations for use as shampoos, hair conditioners, detergents, spot-free rinse solutions, floor and carpet cleaners, scribble remover cleaners, crop protection wetting agents, crop protection adjuvants, and wetting agents for aerosol spray coatings.

[0195] Those skilled in the art will understand that a slight difference between compounds can cause quite different surfactant properties, such that different compounds can be used with different substrates in different applications.

[0196] The following non-limiting embodiments are provided to demonstrate the different properties of different surfactants. In Table 1 below, the abbreviations of the surfactants correlate with their corresponding chemical structures.

[0197]

Table 1-1

[0198]

Table 1-2

[0199] Each of the seven compounds is effective as a surfactant useful as a wetting agent or foaming agent, dispersant, emulsifier and detergent, among other uses.

[0200] Surfactant 1, Surfactant 2, Surfactant 3, Surfactant 6, and Surfactant 7 are cationic. These surfactants are useful for both the above uses and some more special uses, for example, in personal hair care products, for example, in surface treatment, and can also be used to produce water-repellent surfaces.

[0201] Surfactant 4 is zwitterionic. These surfactants are useful as co-surfactants in all of the above uses.

[0202] Surfactant 5 is nonionic and can be used in shampoos, detergents, hard surface cleaners, and a variety of other surface cleaning formulations.

[0203] Examples Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. The critical micelle concentration (CMC) was determined by the Wilhelmy plate method at 23 °C using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate. The dynamic surface tension was determined at 23 °C using a bubble pressure tensiometer (Kruss BP100, Kruss GmbH). The contact angle was determined using an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

[0204] Example 1a: Synthesis of 6-((2-butyl octyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide 2-Butyloctyl 6-(dimethylamino)hexanoate (2.04 mmol, 700 mg) was dissolved in acetonitrile (10 mL). Sodium carbonate (2.44 mmol, 259 mg) was added and the mixture was stirred at room temperature for 10 minutes. Methyl iodide (6.12 mmol, 0.38 mL) was added and the mixture was heated at 40 °C for 24 hours and then cooled to room temperature. The mixture was filtered and the solvent was removed under vacuum to give 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide as a yellow solid in 90% yield. 1 H NMR (500 MHz, DMSO) δ 3.93 (d, J = 5.7 Hz, 2H), 3.29 - 3.22 (m, 2H), 3.04 (s, 9H), 2.34 (t, J = 7.4 Hz, 2H), 1.73 - 1.53 (m, 5H), 1.33 - 1.25 (m, 18H), 0.88 - 0.85 (m, 6H).

[0205] Example 1b: Determination of the critical micelle concentration (CMC) The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide from Example 1a was tested. From the plot of the results shown in Figure 1, the CMC value could not be clearly determined at a concentration as high as 10 mg / mL and the surface tension asymptotically approached a value of about 27 mN / m. Figure 1 is a plot of these results showing the surface tension against the concentration. From the plot of the results, the surface tension at the CMC is about 27 mN / m or less.

[0206] Example 2a: Synthesis of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate 6-(Dimethylamino)hexanoic acid was treated with 2-butyloctan-1-ol and p-toluenesulfonic acid in benzene at 120 °C for 12 h. 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate was isolated as a white waxy solid and recrystallized from acetone in 49% yield. 1 H NMR (500 MHz, DMSO) δ 7.48 (dd, J = 8.4, 0.6 Hz, 2H), 7.12 (dd, J = 8.4, 0.6 Hz, 1H), 3.93 (d, J = 5.7 Hz, 2H), 3.02 - 3.00 (m, 2H), 2.76 (d, J = 5.0 Hz, 6H), 2.37 - 2.25 (m, 6H), 1.59 - 1.53 (m, 5H), 1.25 - 1.29 (m, 18H), 0.87 (td, J = 6.8, 2.7 Hz, 6H).

[0207] Example 2b: Determination of the critical micelle concentration (CMC) The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexan-1-aminium 4-methylbenzenesulfonate from Example 2a was tested. From the change in surface tension at concentrations in water, the CMC was determined to be about 0.97 mmol. The plateau value of the minimum surface tension achievable with this surfactant is about 27 mN / m, i.e., 27 mN / m ± 3 mN / m. Figure 2A is a plot of these results showing surface tension versus concentration. From the plot of the results, the surface tension at the CMC is about 30 mN / m or less.

[0208] Example 2c: Determination of the dynamic surface tension The dynamic surface tension of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate from Example 2a was determined with a bubble pressure tensiometer that measures the change in surface tension of a freshly created air-water interface over time. Figure 2B presents a plot of surface tension versus time showing a surface tension that rapidly drops from about 46 mN / m to about 30 mN / m at time intervals between 10 and 100 ms. At time intervals from 100 to 8,000 ms, the surface tension slowly drops from 30 mN / m to about 27 mN / m, approaching asymptotically the saturation value of the surface tension at the CMC.

[0209] Example 2d: Determination of wettability In addition to surface tension and surface dynamics, the wettability of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate from Example 2a was tested on various surfaces. For example, a hydrophobic substrate, such as polyethylene-HD, exhibits surface wetting with a contact angle of 24.3°. On an oleophobic and hydrophobic substrate, such as Teflon®, the measured contact angle was much smaller at 48.2° than the contact angle of water of 119 o (Table 2).

[0210]

Table 2

[0211] Example 3a: Synthesis of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride 2-Butyloctyl 6-(dimethylamino)hexanoate was treated with 1 equivalent of hydrochloric acid to obtain 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride.

[0212] Example 3b: Determination of the critical micelle concentration (CMC) The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride from Example 3a was tested. From the change in surface tension at the concentration in water, the CMC was determined to be about 27.47 mmol. The minimum surface tension achievable with this surfactant is about 29 mN / m, i.e., 29 mN / m ± 3 mN / m. Figure 3 is a plot of these results showing surface tension versus concentration. From the plot of the results, the CMC value could not be clearly determined at a concentration of 27.4 mmol, and the surface tension asymptotically approached a value of about 29 mN / m.

[0213] Example 4a: Synthesis of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate 2-Butyloctyl 6-(dimethylamino)hexanoate (2.04 mmol, 700 mg) was dissolved in ethyl acetate (30 mL). 1,4-Butanesultone (3.06 mmol, 0.31 mL) was added. The mixture was heated to reflux for 12 hours, and evaporation of the solvent was continued. The resulting white waxy solid was washed with acetone to obtain 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate in 89% yield. 1 H NMR (500 MHz, DMSO) δ 3.93 (d, J = 5.7 Hz, 2H), 3.30 - 3.28 (m, 4H), 2.97 (s, 3H), 2.49 - 2.43 (m, 2H), 2.34 (t, J = 7.4 Hz, 2H), 1.96 - 1.76 (m, 9H), 1.27 - 1.25 (m, 18H), 0.88 - 0.85 (m, 6H).

[0214] Example 4b: Determination of the critical micelle concentration (CMC) The critical micelle concentration (CMC) of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate from Example 4a was tested. From the change in surface tension at the concentration in water, the CMC was determined to be about 0.54 mmol. The Plateau value of the minimum surface tension achievable with this surfactant is about 32 mN / m, i.e., 32 mN / m ± 3 mN / m. Figure 4A is a plot of these results showing surface tension versus concentration. From the plot of the results, the surface tension at the CMC is about 32 mN / m or less.

[0215] Example 4c: Determination of dynamic surface tension The dynamic surface tension of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate from Example 4a was determined with a bubble pressure tensiometer that measures the change in surface tension of a newly created air-water interface over time. Figure 4B presents a plot of surface tension versus time showing that the surface tension rapidly drops from about 66 mN / m to about 36 mN / m at time intervals between 10 and 100 ms. At time intervals from 100 to 8,000 ms, the surface tension slowly drops from 36 mN / m to about 32 mN / m, asymptotically approaching the saturation value of the surface tension at the CMC.

[0216] Example 4d: Determination of wettability In addition to surface tension and surface dynamics, the wettability of 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate from Example 4a was tested on various surfaces. For example, a hydrophobic substrate, such as polyethylene-HD, exhibits surface wetting with a contact angle of 44.4°. On an oleophobic and hydrophobic substrate, such as Teflon®, the measured contact angle was much smaller at 62.2° than the contact angle of water at 119° (Table 3).

[0217]

Table 3

[0218] Example 5a: Synthesis of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide 2-Butyloctyl 6-(dimethylamino)hexanoate was treated with hydrogen peroxide in water at 70 °C for 24 hours to obtain 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide as an oily substance in 90% yield. 1 H NMR (500 MHz, DMSO) δ 3.93 (d, J = 5.7 Hz, 2H), 3.30 - 3.28 (m, 4H), 2.97 (s, 3H), 2.49 - 2.43 (m, 2H), 2.34 (t, J = 7.4 Hz, 2H), 1.96 - 1.76 (m, 9H), 1.27 - 1.25 (m, 18H), 0.88 - 0.85 (m, 6H).

[0219] Example 5b: Determination of critical micelle concentration (CMC) The critical micelle concentration (CMC) of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was tested. From the change in surface tension at concentrations in water, the CMC was determined to be approximately 0.29 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 28 mN / m, i.e., 28 mN / m ± 3 mN / m. Figure 5A is a plot of these results showing surface tension versus concentration. From the plot of the results, the surface tension at the CMC is approximately 28 mN / m or less.

[0220] Example 5c: Determination of dynamic surface tension The dynamic surface tension of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was determined with a bubble pressure tensiometer that measures the change in surface tension of a newly created air-water interface over time. Figure 5B presents a plot of surface tension versus time showing that the surface tension rapidly drops from about 60 mN / m to about 30 mN / m over a time interval from 10 to 1,000 ms. Over the time interval from 1,000 to 8,000 ms, the surface tension slowly drops from 30 mN / m to about 28 mN / m and asymptotically approaches the saturation value of the surface tension at the CMC.

[0221] Example 5d: Determination of wettability In addition to surface tension and surface dynamics, the wettability of 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide from Example 5a was tested on various surfaces. For example, a hydrophobic substrate, such as polyethylene-HD, exhibits surface wetting with a contact angle of 31.6°. On an oleophobic and hydrophobic substrate, such as Teflon®, the measured contact angle was much smaller at 41.5° than the contact angle of water at 119° (Table 4).

[0222] [Table 4]

[0223] Example 6a: Synthesis of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride 2-Butyloctyl 6-(dimethylamino)hexanoate was treated with 1 equivalent of hydrochloric acid to obtain 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride.

[0224] Example 6b: Determination of the critical micelle concentration (CMC) The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride from Example 6a was tested. From the change in surface tension at the concentration in water, the CMC was determined to be about 0.15 mmol. The plateau value of the minimum surface tension achievable with this surfactant is about 27 mN / m, i.e., 27 mN / m ± 3 mN / m. Figure 6A is a plot of these results showing surface tension versus concentration. From the plot of the results, the surface tension at the CMC is about 30 mN / m or less.

[0225] Example 6c: Determination of dynamic surface tension The dynamic surface tension of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride from Example 6a was determined with a bubble pressure tensiometer that measures the change in surface tension of a newly created air-water interface over time. Figure 6B presents a plot of surface tension versus time showing that the surface tension slowly drops from about 69 mN / m to about 29 mN / m over a time interval from 10 to 8,000 ms, showing a slight plateau of about 49 mN / m at a surface elapsed time of 1,000 ms and approaching the saturation value of the surface tension at the CMC.

[0226] Example 6d: Determination of wettability In addition to surface tension and surface dynamics, the wettability of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride from Example 6a was tested on various surfaces. For example, a hydrophobic substrate, such as polyethylene-HD, exhibits surface wetting with a contact angle of 25.8°. On an oleophobic and hydrophobic substrate, such as Teflon®, the measured contact angle was much smaller at 48.7° than the contact angle of water at 119° (Table 5).

[0227] [Table 5]

[0228] Example 7a: Synthesis of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate 6-Aminohexanoic acid (38.11 mmol, 5 g) was dissolved in benzene (50 mL) in a 100 mL round-bottom flask equipped with a Dean Stark trap. p-Toluenesulfonic acid monohydrate (38.11 mmol, 7.25 g) and 2-butyloctanol (38.11 mmol, 7.1 g, 8.5 mL) were added, and the mixture was heated to reflux for 1 week until no further water was separated in the Dean Stark trap. The solvent was removed under vacuum, and the product was crystallized from acetone at -20 °C to remove unreacted residual alcohol. The resulting white waxy solid was filtered to obtain 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate in 82% yield. 1 H NMR (500 MHz, DMSO) δ 7.49 (d, J = 8.0 Hz, 2H), 7.12 (dd, J = 8.4, 0.6 Hz, 2H), 3.93 (d, J = 5.7 Hz, 2H), 2.79 - 2.73 (m, 2H), 2.31 - 2.28 (m, 5H), 1.55 - 1.50 (m, 5H), 1.31 - 1.25 (m, 18H), 0.88 - 0.85 (m, 6H).

[0229] Example 7b: Determination of critical micelle concentration (CMC) The critical micelle concentration (CMC) of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate from Example 7a was tested. From the change in surface tension at concentrations in water, the CMC was determined to be approximately 2.12 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 27 mN / m, i.e., 27 mN / m ± 3 mN / m. Figure 7A is a plot of these results showing surface tension versus concentration. From the plot of the results, the surface tension at the CMC is approximately 30 mN / m or less, and the surface tension is approximately 28.5 mN / m or less at concentrations of approximately 1.0 mmol or more.

[0230] Example 7c: Determination of dynamic surface tension The dynamic surface tension of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate from Example 7a was determined with a bubble pressure tensiometer that measures the change over time of the surface tension of a newly created air-water interface. Figure 7B presents a plot of surface tension versus time showing that the surface tension rapidly drops from about 46 mN / m to about 30 mN / m at time intervals between 10 and 100 ms. At time intervals from 100 to 8,000 ms, the surface tension slowly drops from 30 mN / m to about 27 mN / m and asymptotically approaches the saturation value of the surface tension at the CMC.

[0231] Example 7d: Determination of wettability In addition to surface tension and surface dynamics, the wettability of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate from Example 7a was tested on various surfaces. For example, a hydrophobic substrate, such as polyethylene-HD, exhibits surface wetting with a contact angle of 14.6°. On an oleophobic and hydrophobic substrate, such as Teflon®, the measured contact angle was much smaller at 49.4° than the contact angle of water at 119° (Table 6).

[0232]

Table 6

[0233] Example 8: Flushing liquid One kind of the composition of the present invention contains water, a water-soluble block copolymer, a nonionic surfactant, and a mixture of inorganic salts containing monovalent and / or divalent and / or trivalent ions. A preferred composition of the present invention contains water and a mixture of water-soluble block copolymers. The corresponding amounts of the components named above in the composition can vary. Typically, the composition has, on a wet basis, 0.05 to 20 wt.% of a water-soluble block copolymer, 0.01 to 10 wt.% of a nonionic surfactant, and 0.1 to 20 wt.% of an inorganic salt containing monovalent and / or divalent and / or trivalent ions. The water-soluble monovalent and / or divalent electrolytes are typically used in an amount of about 1 weight percent to about 15 weight percent, or about 1 to 10 weight percent, based on the weight of the aqueous composition (wet basis).

[0234] Some compositions of the present invention contain water and a mixture of water-soluble block copolymers. A preferred composition of the present invention contains a mixture of water, a water-soluble block copolymer polymer, an inorganic salt, and a nonionic surfactant, and essentially does not contain an anionic surfactant.

[0235] The corresponding amounts of the components named above in the composition can vary. Typically, the composition has, on a wet basis, 0.05 to 20 wt% of a water-soluble block copolymer, 0.01 to 10 wt(wit)% of a nonionic surfactant, and 0.1 to 20 wt% of an inorganic salt containing monovalent and / or divalent and / or trivalent ions. The water-soluble monovalent and / or divalent electrolytes are typically used in an amount of about 1 weight percent to about 15 weight percent, or about 1 to 10 weight percent, based on the weight of the aqueous composition (wet basis).

[0236] The corresponding amounts of the components named above in the composition can vary. However, for the water-soluble block copolymer and the nonionic surfactant in the total composition of some embodiments of the present invention, the typical ranges are listed in Table 7 on a wet basis.

[0237]

Table 7

[0238] The water-soluble inorganic salts contain monovalent and / or divalent and / or trivalent ions. The inorganic salt concentrate is typically used in an amount of about 0.01 weight percent to about 20 weight percent, or about 1 weight percent to about 15 weight percent, for example about 1 to 10 weight percent, based on the weight of the aqueous medium.

[0239] Example 9 Flushing fluid Non-limiting examples of the formulations of the present invention include the compositions listed in Table 8.

[0240] [Table 8]

[0241] Example 10 Demulsification of corn oil Non-limiting examples of the formulations of the present invention for use in the demulsification of corn oil include the compositions listed in Table 9.

[0242] [Table 9]

[0243] Example 11: Fluid for improved oil recovery An exemplary composition of an injection fluid suitable for improving the recovery of oil or gas from a well is as follows: 10 (a) 0.01 to 5 wt.% of one or more surfactants of the present invention, (b) an aqueous injection fluid, (c) 0 to 5 wt.% of one or more alkalis, 15 (d) 0 to 1% of one or more thickening agents, (e) 0 to 50 wt.% of one or more co-solvents; (f) 0 to 50 wt.% of one or more co-surfactants, and (g) 0 to 5 wt% of one or more co-surfactants. The aqueous carrier includes, but is not limited to, water, produced brine, river water, synthetic brine, and seawater.

[0244] Example 12 Formulation for Recovering Corn Oil from Distillation Waste Liquid Some exemplary corn oil extraction formulations are summarized in Table 10. Each formulation can be used for demulsifying corn oil.

[0245] The polyglycerol ester is obtained from Lambent Technologies under the product name Lumulse POE(26)Glyc. It contains polymerized glycerol and has an average of 26 moles of ethoxylation per mole of polymerized glycol. The alkyl polyglucoside used is BASF Glucopon® 225 DK, an alkyl polyglucoside that contains a C8 - C10 alkyl group and an average of 1.7 glucose units per mole of alkyl polyglucoside.

[0246] The Peg 400 used is polyethylene glycol having an average molecular weight of 400 daltons. The Peg 400 MO used is polyethylene glycol monooleate having an average molecular weight of 400 daltons. The Peg 400 DO used is polyethylene glycol dioleate having an average molecular weight of 400 daltons.

[0247] The PEG 400 Mono Soyate used is an ester of polyethylene glycol (having an average molecular weight of 400 daltons) and fatty acids derived from soybean oil. Soybean oil is typically a triglyceride that contains fatty acids as follows: myristic acid 0.1%; palmitic acid 11.0%; palmitoleic acid 0.1%, stearic acid 4.0%, oleic acid 23.4%, linoleic acid 53.2%, linolenic acid 7.8%, arachidic acid 0.3%, and behenic acid 0.1%.

[0248] Hydrophobic silica can be utilized as PP - 35 - FGK.

[0249] Hydrophilic silica can be utilized as Sipernat 35.

[0250]

Table 10

[0251] Aspect Aspect 1 is a formulation for hydrocarbon recovery, the following formula:

[0252]

Chemical formula

[0253] (wherein R 1 and R 2 are independently selected from hydrogen, oxygen atoms, and C 1 to C 6 alkyl, C 1 to C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, n is an integer from 2 to 5 (including 2 and 5), R 3 is C 5 to C 12 alkyl, R 4 is C 3 to C 10 alkyl, the terminal nitrogen may be further substituted with R 5 , R 5 is selected from hydrogen, oxygen atoms, and C 1 to C 6 alkyl, C 1 to C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counterion may be associated with the compound. If present, the counterion may be selected from the group consisting of chloride ion, bromide ion, iodide ion, and 4-methylbenzenesulfonate ion) of at least one surfactant, and an aqueous phase.

[0254] Aspect 2 is a formulation according to Aspect 1, further comprising at least one additional surfactant selected from the group consisting of a sulfonate surfactant, an anionic surfactant having a hydrophobic chain of 12 to 24 carbon atoms selected from the group consisting of sulfate surfactants, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

[0255] Aspect 3 is a formulation according to Aspect 1 or Aspect 2, wherein the aqueous phase comprises at least one inorganic salt selected from the group consisting of sodium chloride, sodium sulfate, potassium chloride, magnesium sulfate, and magnesium chloride.

[0256] Aspect 4 is a formulation according to any one of Aspects 1 to 3, further comprising at least one polymer.

[0257] Aspect 5 is a formulation according to Aspect 4, wherein at least one polymer is selected from the group consisting of a cationic polymer containing a quaternary ammonium compound, such as a quaternary diallyldialkylammonium monomer, and / or an anionic polymer containing an anionic monomer selected from the group consisting of acrylic acid, methacrylic acid, and combinations thereof, and the average molecular weight of the anionic polymer ranges from about 50,000 to about 10,000,000.

[0258] Aspect 6 is a formulation according to any one of Aspects 1 to 3, further comprising lecithin or modified lecithin.

[0259] Aspect 7 is a formulation according to any one of Aspects 1 to 6, further comprising at least one water-immiscible solvent.

[0260] Aspect 8 is a formulation according to any one of Aspects 1 to 7, further comprising at least one water-miscible solvent.

[0261] Aspect 9 is a formulation according to any one of Aspects 1 to 8, further comprising at least one gas selected from the group consisting of air, nitrogen, carbon dioxide, and natural gas.

[0262] Aspect 10 is a formulation according to Aspects 1 to 9, further comprising at least one additive selected from the group consisting of hydrogen chloride, ammonium salts, ammonium bicarbonate, ammonium carbonate or ammonium hydroxide, alcohol, crosslinking agent, disintegration retardant, particles, propant, gas component, disintegration aid, oxygen scavenger, alcohol, scale inhibitor, corrosion inhibitor, fluid loss additive, biocide / bactericide, friction reducer and latex.

[0263] Aspect 11 is a formulation according to any of Aspects 1 to 10, wherein the surfactant is of the following formula:

[0264]

Chemical formula

[0265] 6-((2-Butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula:

[0266] Aspect 12 is a formulation according to any of Aspects 1 to 10, wherein the surfactant is of the following formula:

[0267]

Chemical formula

[0268] 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the formula:

[0269] Aspect 13 is a formulation according to any of Aspects 1 to 10, wherein the surfactant is of the following formula:

[0270]

Chemical formula

[0271] A formulation according to any of Aspects 1 to 10, which is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride.

[0272] Aspect 14 is such that the surfactant is of the following formula:

[0273]

Chemical formula

[0274] A formulation according to any of Aspects 1 to 10, which is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the following formula:

[0275] Aspect 15 is such that the surfactant is of the following formula:

[0276]

Chemical formula

[0277] A formulation according to any of Aspects 1 to 10, which is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the following formula:

[0278] Aspect 16 is such that the surfactant is of the following formula:

[0279]

Chemical formula

[0280] A formulation according to any of Aspects 1 to 10, which is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the following formula:

[0281] Aspect 17 is such that the surfactant is of the following formula:

[0282]

Chemical formula

[0283] The composition according to any one of aspects 1 to 10, which is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having

[0284] Aspect 18 is a method for recovering hydrocarbons, comprising the steps of preparing at least one composition of any one of aspects 1 to 17, injecting at least one composition into a well, and recovering a material from the well after the step of injecting the composition into the well.

[0285] Aspect 19 is a method for recovering hydrocarbons, comprising the steps of preparing at least one composition of any one of aspects 1 to 17, mixing the composition with a material containing bio-oil, and recovering bio-oil from the mixture.

[0286] Aspect 20 is the method according to aspect 19, wherein the material containing bio-oil is distillation waste liquid.

[0287] Aspect 21 is a method for recovering hydrocarbons, comprising the steps of introducing a foaming fluid composition into an oil or gas well, and performing operations with the foaming fluid composition, wherein the foaming composition comprises a base fluid containing an oil-based or water-based fluid, a gas, and the following formula:

[0288]

Chemical formula

[0289] (In the formula, R 1 and R 2 are independently selected from hydrogen, an oxygen atom, and C 1 to C 6 alkyl, and C 1 to C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl, or sulfonate, n is an integer from 2 to 5 (including 2 and 5), and R 3is C 5 ~C 12 is alkyl, and R 4 is C 3 ~C 10 is alkyl, and the terminal nitrogen may be further substituted with R 5 and R 5 is hydrogen, an oxygen atom, and C 1 ~C 6 selected from alkyl, and C 1 ~C 6 alkyl may be substituted with carboxylate, hydroxyl, sulfonyl or sulfonate, and an optional counter ion may be associated with the compound, and if present, the counter ion may be selected from the group consisting of chloride ion, bromide ion, iodide ion and 4-methylbenzenesulfonate ion) containing at least one surfactant.

[0290] Aspect 22 is the method of aspect 21, wherein the operation is selected from the group consisting of gas lift operations, drilling operations, finishing operations, stimulation operations, fracturing operations, injection operations, enhanced oil recovery operations, and combinations thereof.

[0291] Aspect 23 is that the surfactant is of the following formula:

[0292]

Chemical formula

[0293] is 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having

[0294] Aspect 24 is that the surfactant is of the following formula:

[0295]

Chemical formula

[0296] The formulation of embodiment 21 or embodiment 22, which is 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate.

[0297] Embodiment 25 is such that the surfactant has the following formula:

[0298]

Chemical formula

[0299] The formulation of embodiment 21 or embodiment 22, which is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride.

[0300] Embodiment 26 is such that the surfactant has the following formula:

[0301]

Chemical formula

[0302] The formulation of embodiment 21 or embodiment 22, which is 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate.

[0303] Embodiment 27 is such that the surfactant has the following formula:

[0304]

Chemical formula

[0305] The formulation of embodiment 21 or embodiment 22, which is 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide.

[0306] Embodiment 28 is such that the surfactant has the following formula:

[0307]

Chemical formula

[0308] The composition of embodiment 21 or embodiment 22, which is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having

[0309] Embodiment 29 is such that the surfactant has the following formula:

[0310] [Chemical formula]

[0311] The composition of embodiment 21 or embodiment 22, which is 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having

Claims

**Claim 1** A formulation for hydrocarbon recovery, comprising: The following formula: 【Chemical 1】 6-((2-Butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having The following formula: [Chemical Formula 2] 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having The following formula: [Chemical Formula 3] 6-((2-Butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having The following formula: 【Chemical 4】 4-((6-((2-Butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having The following formula: 【Chemical Formula 5】 2-Butyloctyl 6-(dimethylamino)hexanoate N-oxide having The following formula: 【Chemical Formula 6】 6-((2-Butyloctyl)oxy)-6-oxohexane-1-aminium chloride having, and The following formula: 【Chemical Formula 7】 6-((2-Butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate having, at least one of a surfactant, and An aqueous phase. **Claim 2** The formulation according to claim 1, further comprising at least one additional surfactant selected from the group consisting of anionic surfactants having a hydrophobic chain of 12 to 24 carbon atoms, cationic surfactants, nonionic surfactants, and zwitterionic surfactants, selected from the group consisting of sulfonate surfactants and sulfate surfactants. **Claim 3** The formulation according to claim 1, wherein the aqueous phase comprises at least one inorganic salt selected from the group consisting of sodium chloride, sodium sulfate, potassium chloride, magnesium sulfate, and magnesium chloride. **Claim 4** The formulation according to claim 1, further comprising at least one polymer selected from the group consisting of quaternary ammonium compounds, anionic surfactants, and combinations thereof, wherein the average molecular weight of the polymer ranges from 50,000 to 10,000,000. **Claim 5** The formulation according to claim 1, further comprising lecithin or modified lecithin. **Claim 6** The formulation according to claim 1, further comprising at least one water-immiscible solvent. **Claim 7** The formulation according to claim 1, further comprising at least one water-miscible solvent. **Claim 8** The formulation according to claim 1, further comprising at least one gas selected from the group consisting of air, nitrogen, carbon dioxide, and natural gas.

9. The formulation according to claim 1, further comprising at least one additive selected from the group consisting of hydrogen chloride, ammonium salts, ammonium bicarbonate, ammonium carbonate, ammonium hydroxide, alcohols, crosslinking agents, disintegration retardants, particles, proppants, gas components, disintegration aids, oxygen scavengers, scale inhibitors, corrosion inhibitors, fluid loss additives, biocides / fungicides, friction reducers, and latex.

10. A method for recovering hydrocarbons, comprising: preparing at least one formulation according to claim 1; injecting at least one formulation into a well; and recovering materials from the well after injecting the formulation into the well.

11. A method for recovering hydrocarbons, comprising: preparing at least one formulation according to claim 1; mixing the formulation with a material containing bio-oil; and recovering bio-oil from the mixture.

12. The method according to claim 11, wherein the material containing bio-oil is distillation waste liquid.

13. A method for recovering hydrocarbons, comprising: introducing a foamed fluid composition into an oil or gas well and working with the foamed fluid composition, the foamed fluid composition comprising: a base fluid comprising an oil-based or water-based fluid; a gas; and 6-((2-butyloctyl)oxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the following formula: [Chemical Formula 8] 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium 4-methylbenzenesulfonate having the following formula: 【Chemical Formula 9】 6-((2-butyloctyl)oxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the following formula: 【Chemical Formula 10】 4-((6-((2-butyloctyl)oxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the following formula: 【Chemical 11】 2-butyloctyl 6-(dimethylamino)hexanoate N-oxide having the following formula: 【Chemical Formula 12】 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium chloride having the following formula: 【Chemical 13】 ​ ​ 【Chemical 14】 Surfactant containing at least one of 6-((2-butyloctyl)oxy)-6-oxohexane-1-aminium 4-methylbenzenesulfonate, A method comprising.

14. The method according to claim 13, wherein the operation is selected from the group consisting of gas lift operations, drilling operations, finishing operations, stimulation operations, fracturing operations, injection operations, enhanced oil recovery operations, and combinations thereof.

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