Surfactants for oil and gas production

Abstract

Surfactants used in formulations and processes suitable for hydrocarbon recovery. These formulations include those suitable for fracking, enhancing oil or gas recovery, and recovering and / or producing bio-based oils.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Patent Application No. 18 / 795,160, filed on August 5, 2024, which in turn claims priority to U.S. Patent Provisional Application No. 63 / 531,213, filed on August 7, 2023, and the full disclosure thereof is incorporated by reference in its entirety.

[0002] This disclosure relates to surfactants for use in the production and recovery of hydrocarbons, including oil and gas from wells and oil from bio-based processes. Such surfactants may include siloxane derivatives of amino acids, wherein the siloxane derivative has surface-active properties. [Background technology]

[0003] Surfactants (molecules with surface-active properties) are widely used in the commercial production of oil and natural gas. These formulations may include a variety of liquids, emulsions, and foams used for the recovery of hydrocarbons from soil and bio-based sources. Both oil and natural gas may be found in contact with water or water-soluble substrates, and therefore surfactants may be included in formulations to improve the recovery of oil and / or gas. Ideally, formulations for such production and recovery processes should be easy to manufacture, deploy, and, in practice, reuse.

[0004] Surfactants may be uncharged, amphoteric, cationic, or anionic. In principle, any class of surfactant (e.g., cationic, anionic, nonionic, amphoteric) is suitable, but a formulation may contain a combination of two or more surfactants from two or more surfactant classes.

[0005] In most cases, surfactants are amphiphilic molecules that have a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can be adsorbed at interfaces such as between two liquids, between gas and liquid, or between solid and liquid. In systems containing relatively polar and relatively nonpolar components, the hydrophobic tail preferentially interacts with the relatively nonpolar component, while the hydrophilic head preferentially interacts with the relatively polar component. At the interface between water and oil, the hydrophilic head preferentially extends into the water, while the hydrophobic tail preferentially extends into the oil. When added to a gas-water interface, the hydrophilic head preferentially extends into the water, while the hydrophobic tail preferentially extends into the gas. In the presence of a surfactant, at least some of the intermolecular interactions between water molecules are disrupted, and at least some of the interactions between water molecules are replaced by generally weaker interactions between at least some of the water molecules and the surfactant. This can result in a decrease in surface tension, which can help stabilize the interface between materials with different physical forms.

[0006] At sufficiently high concentrations, surfactants can form aggregates that act to limit the exposure of their hydrophobic tails to polar solvents. One such aggregate is a micelle. In a typical micelle, the molecules are arranged spherically, with the hydrophobic tail of the surfactant preferentially located inside the sphere and the hydrophilic head preferentially located outside the micelle, which preferentially interacts with more polar solvents. The effect a given compound has on surface tension, as well as the concentration at which it forms micelles, can serve as a definition of the surfactant's properties.

[0007] The development and production of crude oil from oil-bearing formations may involve up to three stages: primary, secondary, and tertiary (or enhanced) recovery. During primary recovery, natural energy present in the formation (e.g., water, gas) and / or gravity push the oil into the production well. As oil is produced from the oil-bearing formation, the pressure and / or temperature within the formation may decrease. Artificial oil extraction techniques (e.g., pumps) may be used to bring the oil to the surface. Only about 10 percent of the original reserves (OOIP) of the reservoir are typically produced during primary recovery. Secondary recovery techniques are used to extend the production life of the oil field and generally involve the process of injecting a displacement fluid, such as water (watering), to replace the oil and push it into the production well.

[0008] Secondary recovery techniques typically result in the recovery of an additional 20-40 percent of the OOIP (Out-of-Potential Intake) in the reservoir. However, even if water treatment is continued indefinitely, more than half of the OOIP usually remains unrecovered. Insufficient 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 flushing of the injected water through the formation, and other factors contribute to the inefficiency. Therefore, significant amounts of oil remain in the reservoir with both primary and secondary techniques.

[0009] When much of the easily produced oil has already been recovered from the oilfield, producers use tertiary or enhanced oil recovery (EOR), a technique that has the potential to recover 30–60 percent or more of the OOIP in the reservoir. Three main categories of EOR: heat recovery, gas injection, and chemical techniques are commercially successful. In heat recovery, heat is introduced (e.g., steam injection) to reduce the viscosity of the crude oil and improve its ability to flow through the reservoir. In gas injection, nitrogen, carbon dioxide, or other gases that spread through the reservoir are used to push additional oil into the production well. Other gases that dissolve in the oil reduce viscosity and improve fluidity. In chemical techniques, surfactants are injected (surfactant injection) to reduce the surface tension that prevents or inhibits oil droplets from moving through the reservoir, or polymers are injected into oil present in the formation to make it more easily mobile through the formation.

[0010] Chemical techniques can be used before, during, or after the implementation of primary and / or secondary recovery techniques. Chemical techniques can also complement other EOR techniques. Surfactant techniques may include surfactant polymer (SP) techniques and alkaline surfactant polymer (ASP) techniques. In the SP technique, water and / or brine containing about 1 wt% surfactant and -0.1 wt% polymer is injected into the reservoir. The ASP technique includes alkali in addition to the components used in the SP technique. An ASP system typically contains about 0.5 to 1 wt% alkali, -0.1 to 1 wt% surfactant, and about 0.1 to 1 wt% polymer. Typically, SP or ASP attack methods are followed by the injection of a replacement fluid, such as a water attack and / or polymer extrusion fluid. The choice between SP and ASP depends on the acid value of the oil to be recovered, the concentration of divalent cations in the brine of the reservoir, the economic conditions of the project, the ability to perform water softening or desalination, and other factors. Alkali sequestrate divalent cations in the brine of the formation, thereby reducing the adsorption of surfactants through the formation during replacement. Alkali also produce anionic surfactants (sodium naphthenate soap) in situ in the formation by reacting with naphthenic acid, which is naturally present in crude oil. The use of relatively inexpensive alkalis reduces the retention of surfactants and therefore reduces the amount of surfactant required, resulting in a reduction in overall costs. Alkali can also improve the water absorption rate by helping to change the wettness of the formation to a more water-wet state.

[0011] Another EOR technique, "wetness modification," involves introducing surfactants into the reservoir, sometimes combined with changes in electrolyte concentration to replace adsorbed oil by inducing spontaneous water absorption onto the reservoir rock. This technique does not necessarily require low interfacial tension between the oil and aqueous phases, or the formation of a microemulsion phase. It also does not require good flushing efficiency of the displacement fluid, and therefore can be useful in carbonate reservoirs that are usually not very suitable and can be fractured. Surfactants used in SP and ASP techniques have also shown usefulness in wetness modification.

[0012] After injection into an oil-containing formation, the surfactant system draws up crude oil and brine from the formation, forming a multiphase microemulsion in situ. Once complete, the microemulsion becomes miscible with the reservoir's crude material 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 give mobility to discontinuous crude oil droplets in the formation, creating an oil reservoir where both oil and water flow as a continuous phase. IFT varies with salinity, surfactant composition, crude oil composition, formation temperature, and other variable factors. For anionic surfactants, there exists an optimal salinity where the microemulsion solubilizes equal amounts of oil and water, and the microemulsion exhibits an IFT approximately equal to that of oil and brine. Ultra-low IFT generally exists only in 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 testing against crude oil from target reservoirs and can involve considerable effort to find suitable surfactants and other components, such as polymers, electrolytes, cosurfactants, and cosolvents."

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

[0015] Due to the concentration effect that dry grinding has on the oil fraction, corn oil extracted from high-viscosity distillation wastewater has become a profitable co-product in the ethanol industry. Removing 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 result in a valuable co-product but also improve the quality of DDGS.

[0016] Current methods for extracting corn oil from high-viscosity distillation wastewater include solvent extraction (mostly hexane) and decantation. Hexane extraction is effective but energy-intensive and requires significant capital investment. Decantation requires less capital investment and has the potential to be just as effective as hexane extraction.

[0017] Decantation using centrifugal separation has the advantage of the density difference between the oil and aqueous phases, which creates buoyancy for the oil suspended in the solution. For buoyancy to be strong enough to overcome interfacial interactions and surface friction acting on the oil, individual oil droplets must be large enough to generate sufficient force. Current separation devices used in industry can separate particles as small as 20 micrometers in diameter. The success of current corn oil decantation is heavily dependent on upstream processing conditions. Processes using high temperatures, high or low pH, finer grinds, and longer holding periods tend to show increased oil yield. These harsh conditions may not be preferable for extracting oil for human or animal consumption, and therefore the conditions can negatively impact the nutritional and sensory properties of the final product. [Overview of the project]

[0018] This disclosure provides formulations useful for several applications from mixtures of oil-based fuels and aqueous media used in the extraction of oil and natural gas from wells, and in bio-based processes for producing hydrocarbon fuels such as biodiesel. These products may be formulated to contain one or more surfactants from one or more surfactant classes disclosed herein. Surfactants can be used as emulsifiers, wetting agents, dispersants, and / or agents to improve the recovery and / or separation of hydrocarbons from water-containing environments.

[0019] This disclosure provides surfactants for use in the production of oils and gases, in the form of siloxane derivatives of amino acids having surface-active properties. The amino acids may be natural or synthetic amino acids, or may be obtained via ring-opening reactions of molecules such as lactams, e.g., caprolactam. The amino acids may be functionalized with different types of siloxane groups to form compounds having surface-active properties. Characteristically, these compounds may have the ability to reduce the critical micelle concentration (CMC) and / or the surface tension of liquids.

[0020] This disclosure relates to fracking fluid formulations, which are of formula I or II

[0021] [ka]

[0022] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12 The group consisting of linkers may be selected, where the additional surfactant molecule of formula I is the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. One or more surfactant molecules having the structure, And optionally, polymers or viscoelastic surfactants. The present invention provides a fracking fluid formulation containing the above.

[0023] For clarity, in the cases disclosed herein and in any of the formulations provided herein, the molecule of formula II has the following structure: Formula I - Linker - Formula I may represent a composition, and one molecule of Formula I may be the same as or different from another molecule of Formula I. In this exemplary composition, the linker is R in Formula I 3 , C1 - C 12 linker.

[0024] Furthermore, the surfactant molecules provided by the present disclosure are those compounds of Formula I or II in which R 1 and R 2 are methyl. Other surfactant molecules provided by the present disclosure are compounds of Formula I or II in which n and / or z is 5.

[0025] Specifically, R 3 may be selected from the group consisting of C2 - C 10 alkenyl, C2 - C 10 alkynyl, C2 - C 12 ester, C1 - C 10 hydroxyl, benzyl, C2 - C 12 alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3 - C8 carboxylic acid, C1 - C5 alkylbenzoic acid, and a three - carbon linker bonded to a second molecule of Formula I, and the second molecule of Formula I is the same as the first molecule of Formula I.

[0026] More specifically, R 3 may be selected from the group consisting of the following formulas.

[0027]

Chemical formula

[0028] Furthermore, the use of the compounds of Formula I or II described herein as surfactants in the fracturing fluid formulations described herein is disclosed. The present disclosure relates to an improved fluid for oil recovery, which is of Formula I or II

[0029]

Chemical formula

[0030] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12 The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. One or more surfactant molecules having the structure, Linear, crosslinked and / or block copolymers; and / or Optional viscoelastic surfactants; and Optionally selected cosurfactants The present invention further provides oil recovery fluids, including those mentioned above.

[0031] Further disclosures include the use of compounds of formula I or II described herein as surfactants in improved oil recovery formulations described herein. This disclosure also relates to formulations for recovering biologically produced oils, which are of formula I or II

[0032] [ka]

[0033] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12 The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. One or more surfactant molecules having the structure; and water The present invention provides a compound containing the above.

[0034] Further disclosure relates to the use of compounds of formula I or II described herein as surfactants in formulations for recovering biologically produced oils as described herein.

[0035] This disclosure further relates to formulations used in a mixture of fracking fluid and oil or natural gas, wherein formula I or II

[0036] [ka]

[0037] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12 The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. One or more surfactant molecules having the structure, and water, as well Selectively gas The present invention provides a formulation containing the above.

[0038] Furthermore, the use of compounds of formula I or II described herein as surfactants in formulations comprising a mixture of the fracking fluid described herein and oil or natural gas is disclosed herein.

[0039] The above-mentioned and other features of this disclosure, as well as the methods for achieving them, will become more apparent and better understood by referring to the following descriptions of embodiments in conjunction with the accompanying drawings. [Brief explanation of the drawing]

[0040] [Figure 1] Figure 1 shows a plot of surface tension versus concentration of surfactant 1, as described in Example 2b. [Figure 2] Figure 2 shows a plot of surface tension versus concentration of surfactant 2 as described in Example 3b. [Figure 3] Figure 3 shows a plot of surface tension versus concentration of surfactant 3, as described in Example 4b. [Figure 4] Figure 4 shows a plot of surface tension versus concentration of surfactant 4 as described in Example 5b. [Figure 5] Figure 5 shows a plot of surface tension versus concentration of surfactant 5 as described in Example 6b. [Figure 6] Figure 6 shows a plot of surface tension versus concentration of surfactant 6 as described in Example 7b. [Figure 7] Figure 7 shows a plot of surface tension versus concentration of surfactant 7 as described in Example 8b. [Figure 8] Figure 8 shows a plot of surface tension versus concentration of surfactant 8 as described in Example 9b. [Figure 9] Figure 9 shows a plot of surface tension versus concentration of surfactant 9 as described in Example 11b. [Figure 10] Figure 10 shows a plot of surface tension versus concentration of surfactant 10 as described in Example 10b. [Figure 11] Figure 11 shows a plot of surface tension versus concentration of the surfactant described in Comparative Example A2. [Modes for carrying out the invention]

[0041] As used herein, the phrase "within any range using these endpoints" means literally that any range may be selected from any two of the values ​​listed before the phrase, regardless of whether the values ​​are at the lower or higher end of the enumeration. For example, a pair of values ​​may be selected from the two lower values, the two higher values, or the lower value and the higher value.

[0042] As used herein, the term "alkyl" means any saturated carbon chain, which may be straight or branched. As used herein, the term “surface-active” means that the compound in question can reduce the surface tension and / or interfacial tension with a medium in which it is at least partially dissolved, thereby being at least partially adsorbed to a gas-liquid interface and / or other interface. The term “surfactant” may be applied to such compounds.

[0043] Wherever a term is used explicitly, or otherwise implicitly, in this specification, the term “composition” may be used interchangeably with the term “formulation.” With regard to the terminology of inaccuracy, the terms “about” and “approximately” may be used interchangeably and mean a measurement that includes the stated measurement and any measurement that is reasonably close to the stated measurement. A measurement that is reasonably close to the stated measurement deviates from the stated measurement by a reasonably small amount that is understood and readily verifiable by a person skilled in the art. Such deviations may be due, for example, to measurement errors or small adjustments made to optimize performance. Where a person skilled in the art would determine that the value relating to such a reasonably small difference is not readily verifiable, the terms “about” and “approximately” may be understood to mean plus or minus 15% of the stated value, for example plus or minus 15%, plus or minus 12%, plus or minus 10%, plus or minus 9%, plus or minus 8%, plus or minus 8%, plus or minus 7%, plus or minus 6%, plus or minus 5%, plus or minus 4%, plus or minus 3%, plus or minus 2%, and further plus or minus 1%, etc.

[0044] This disclosure provides formulations for use in the production and / or recovery of hydrocarbons. Such formulations include fracking fluids and improved oil recovery (IOR) injection fluids; A compound used to increase natural gas production; Compounds for recovering bio-oil from sources such as distillation wastewater; It also includes vegetables, fruits, and nuts.

[0045] I. Fracking Fluids To recover hydrocarbons from hydrocarbon-containing subsurface geological structures, wells are drilled into the geological formations, and hydrocarbon channels are created from reservoirs within the formations to the surface. However, stimulation techniques known as hydraulic fracturing often require improvements to the hydrocarbon channels and recovery from oil or gas wells.

[0046] In hydraulic fracturing, a specific fluid is injected into a target rock formation at a rate exceeding the rate at which it can be dispersed by the natural permeability of the rock. The specific fluid used in this technique is called the fracturing fluid. The fluid increases in pressure until such pressure exceeds the strength of the rock. When this occurs, the rock breaks down, and so-called "fracturing" begins. As injection continues, the fracturing grows in length, width, and height. The fracturing produced by the application of this stimulation technique creates a conduit to a well for hydrocarbons.

[0047] Ideally, the fracturing fluid should minimize the transfer of pressure loss in the well pipe during placement and should have sufficient viscosity to carry the propane material that prevents fracturing by occlusion. Furthermore, the fracturing fluid should have a minimum leakage rate to avoid the fluid transferring into the formation rock, in order to create and spread the fracturing, and should decompose so that no residue remains that could prevent the precise flow of hydrocarbons into the well.

[0048] Some fracturing fluids include: (a) an aqueous medium, and (b) a thickening agent composition comprising (i) a water-soluble or water-dispersible interpolymer having a pendant hydrophobic group chemically bonded to itself, (ii) a nonionic surfactant having hydrophobic groups (may be more) capable of associating with the hydrophobic groups on the organic polymer, and (iii) a water-soluble electrolyte. In addition, the fluid preferably contains a stabilizing amount of thiosulfate. As an example, an interpolymer of acrylamide and dodecyl acrylate has been used in combination with a nonionic surfactant (10-14 HLB) to thicken a diluted aqueous solution of KCl and sodium thiosulfate, and the aqueous solution has had excellent properties for use as a high-temperature hydraulic fracturing fluid. See, for example, PCT application International Publication 87 / 01758 entitled "Hydraulic Fracturing Method and Compositions".

[0049] Some of the fracturing fluids include aqueous liquid media with increased low shear viscosity, obtained by dispersing (1) a water-soluble polymer having pendant hydrophobic groups, such as acrylamide dodecyl acrylate copolymer, and (2) a water-dispersible surfactant, such as sodium oleate or dodecyl polyethylene oxyglycol monoether, in an aqueous medium. See, for example, U.S. Patent No. 4,432,881, entitled “Water-Dispersible Hydrophobic Thickener”. At least some of the surfactants of the present invention listed herein may be included in these formulations.

[0050] Many fracking fluids contain water, a thickener, a polymeric gel, and a surfactant. Alternative fracking fluids may contain a viscoelastic surfactant instead of a polymeric gel. 1. Polymeric gel Polymeric gels may consist of one or more linear polymers, crosslinked polymers, and / or coblocked polymers.

[0051] Useful linear polymers include, but are not limited to, guar, guar derivatives, hydroxyethylcellulose, hydroxyethylcellulose derivatives, and mixtures thereof.

[0052] Useful crosslinked polymers include, but are not limited to, polymers crosslinked with borate ions, zirconate ions, and / or titanate ions. Useful coblock polymers include, but are not limited to, alkylphenol polyethylene oxide condensates, for example, alkylphenol condensation products having an alkyl group containing about 6 to about 20 carbon atoms in a linear or branched configuration and ethylene oxide, where the ethylene oxide is present in an amount equal to about 1 to about 10 moles of ethylene oxide per mole of alkylphenol. The alkyl substituents in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane.

[0053] 2. Surfactants The formulations of the inventions of this disclosure include one or more surfactants, also known as a surfactant system. The surfactant system is included to emulsify the composition and / or to act as an auxiliary agent. The surfactant system may include at least one surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, or a nonionic surfactant, and optionally at least one other surfactant, which may be an amphoteric surfactant, a zwitterionic 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 and should not unduely impair the stability, aesthetics, or performance of the product.

[0054] Suitable surfactants used in the fracking fluids of this disclosure are those of formula I or II

[0055] [ka]

[0056] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. It contains one or more surfactants and / or copolymers.

[0057] Specifically, R 3 C2~C 10 Alkenyl, C2~C 10 Alkinyl, C2~C 12 Ester, C1~C 10 Hydroxyl, benzyl, C2-C 12 The second molecule of formula I may be selected from the group consisting of alkoxyalkyl ethers, alkyl phosphates, alkyl phosphonates, C3-C8 carboxylic acids, C1-C5 alkylbenzoic acids, and a 3-carbon linker bonded to the second molecule of formula I, wherein the second molecule of formula I is the same as the first molecule of formula I.

[0058] More specifically, R 3 The following set of formulas may be selected.

[0059] [ka]

[0060] A suitable surfactant or co-surfactant may contain one or more of the surfactants 1 to 12 described herein. The concentration of the surfactant system in the fracking fluid formulation may be in the range of about 20% by weight or more, about 30% by weight or more, about 40% by weight or more, or about 50% by weight or less, about 60% by weight or less, about 70% by weight or less, or about 80% by weight or less of the composition, or within any of these endpoints.

[0061] 3. Thickening agent The fracking fluid formulation may include a water-soluble polymer having a pendant hydrophobic group, such as an acrylamide dodecyl acrylate copolymer.

[0062] 4. Viscoelastic surfactants Viscoelastic surfactants are generally defined as substantially polymer-free reagents. Various viscoelastic surfactant fluids are disclosed, for example, in U.S. Patents 4,615,825, 4,725,372, 4,735,731, Canadian Patent No. 1,298,697, U.S. Patents 5,551,516, 5,964,295, 5,979,555, and 6,232,274. One 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-erucyl-N,N-bis(2-hydroxyethyl)-N-methylammonium chloride, and isopropanol and brine, the brine comprising 3 wt% ammonium chloride and 4 wt% potassium chloride.

[0063] 5. Other additives Optional additives include compounds that can reduce or mitigate the impact of solids, such as sand, that may become incorporated into the recovered oil. These compounds include clay-stabilizing or sand-stabilizing materials. Suitable clay-stabilizing or sand-stabilizing materials include epoxy resins and polyfunctional cationic polymers, such as poly(N-acrylamidomethyltriethylammonium chloride) or poly(vinylbenzyltrimethylammonium chloride).

[0064] Other optional raw material components that can be added to the fluid of the present invention include, but are not limited to, corrosion inhibitors, oxygen absorbers, and disinfectants. 6. Manufacturing Method The method includes the step of combining a surfactant or surfactant system, polymer and / or a viscoelastic surfactant with water. This step may also include the step of adding any of the above-mentioned additives. The aforementioned components and compounds may be added one or more times in any order, in any amount, and in one or more individual steps, for example, whole or partially. In some methods using fracking fluids, a significant amount of water is combined with the fluid when injected into the well.

[0065] 7. How to use The fracking fluid formulations of this disclosure may be in liquid form with the essential components solubilized therein at room temperature and atmospheric pressure.

[0066] The concentrated fracking fluid is intended to be mixed with an aqueous medium before and / or during use of the fluid. The concentrated formulation may be added to the tank before, simultaneously with, or after the addition of the aqueous medium (water) to the tank. The concentrated fluid may be significantly diluted upon injection into the well, where the well itself already contains water. In some cases, the fluid is injected into the well, followed by the introduction of water, or in some cases, additional water.

[0067] The water content in the diluted fracking formulations of this disclosure may range from about 75% by weight or more, to about 90% by weight or more, about 99% by weight or more, or about 99.9% by weight or more, based on the total weight of the diluted composition, and ultimately depends on the amount of water required to dilute the fracking raw material components in the concentrated inventive formulations of this disclosure to a desired concentration as a ready-to-use composition.

[0068] When mixed with an aqueous medium and diluted in it, the components of the fluid are intended to be evenly distributed within the aqueous medium. II. Compounds for Improved Oil Recovery (IOR) Crude oil and / or naturally occurring gases reside within pores in certain underground rocks. Typically, the initial or primary recovery of crude oil and / or naturally occurring gases involves using the pressure within the oil reservoir to push the crude oil upward through the well. During primary recovery, only a small percentage of crude oil is extracted at any given location; most oil reservoirs typically yield only about 10% to 30% of the crude oil.

[0069] Additional oil can be produced as secondary recovery using known methods such as water pressure or gas injection. Secondary recovery is relatively inexpensive and effective for producing an additional 5% to 20% of the original crude oil in the reservoir. In secondary recovery, pressure is applied to the oil reservoir to push the crude oil upward through the well. However, the 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 extremely strong capillary forces. Due to cost, many wells are not used after the primary and secondary recovery processes are completed.

[0070] Additional processes that increase the amount of oil extracted are sometimes called enhanced oil recovery (EOR), improved oil recovery (IOR), or tertiary recovery. EOR plays a role in improving oil replacement by reducing the interfacial tension (IFT) between oil and water and by restoring formation pressure to extract crude oil. The three main types of EOR include chemical or caustic methods, miscible replacement using carbon dioxide injection or hydrocarbon injection, and heat recovery using vapor methods or in-situ combustion.

[0071] Another method for improving oil recovery from wells is the miscible gas method. The miscible gas method, using carbon dioxide, can reduce the viscosity of crude oil present in the subsurface to increase the flow of hydrocarbons into the production well. Acting as a solvent to reduce the viscosity of the crude oil, carbon dioxide is an effective and relatively inexpensive miscible gas. During the procedure of the miscible carbon dioxide method, carbon dioxide is typically in a liquid and / or supercritical phase. A method used to increase the effectiveness of the miscible gas method is to add foaming surfactants to the process.

[0072] In miscible displacement, a miscible gas is introduced into the oil reservoir. Carbon dioxide is the most commonly used because the gas reduces oil viscosity and is not as expensive as liquefied petroleum gas. Heat recovery involves inducing heat into the oil reservoir to reduce the viscosity of the crude oil, thereby causing it to flow towards the well. During heat 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 involve different reactions such as cracking and dehydrogenation. However, assembling the massive equipment and piping systems to generate and transport large amounts of carbon dioxide is costly, and many oil fields are located in places where assembling such equipment is not feasible. Also, carbon dioxide is generally suitable for light oil fields. Heat recovery is only suitable for certain oil fields, especially those that are shallow and where heavy oil seeps, but the injection may be followed by cheaper fluids such as high-viscosity water, and then plain water. The injection of surfactants, high-viscosity water, and water is involved in the replacement of crude oil into production wells.

[0073] Another tertiary recovery process involves chemical or caustic trapping. This type of EOR uses a water trapping method containing surfactants, polymers, and / or caustic compounds. The water trapping method reduces IFT and pushes the crude oil away from the rock. This crude oil, in a stationary form as droplets trapped in capillaries, can be made mobile by injection, which is a water trapping method using surfactants. The surfactants interact with the crude oil to form microemulsions that reduce the capillary trapping force to a very low level. Once mobile, the crude oil forms a growing oil reservoir where almost no oil remains in the trapped portion of the reservoir. After the water trapping, the injection may be followed by a cheaper fluid such as high-viscosity water, and then plain water. The injection of surfactants, high-viscosity water, and water is accompanied by the replacement of the crude oil into the production well. Several patents and publications discuss methods of enhanced oil recovery using surfactants.

[0074] The present invention involves the use of various amphoteric surfactants, including but not limited to alkylamidopropyl betaine sulfonates, alkyldimethyl betaine sulfonates, alkylhydroxysultaine sulfonates, alkylsulsulbetaine sulfonates, and alkylamine oxide sulfonates, as low-adsorption surfactants for applications including but not limited to IOR, drilling, viscoelastic surfactants, acid treatment, crushing, foaming, and production. The present invention involves the use of sulfonating agents, which react with the double bonds of certain amphoteric surfactants, including but not limited to alkyleneamidopropyl betaine, alkylenedimethyl betaine, alkylenehydroxysultaine, alkylenesulsultaine, and alkyleneamine oxides, to produce the corresponding sulfonated amphoteric surfactants. It has been found that sulfonated amphoteric surfactants provide ultra-low interfacial tension (IFT), viscoelastic properties, compatibility with brines containing large amounts of salt and divalent ions, and low adsorption to reservoir rocks. Some embodiments of the present invention involve the use of various amphoteric surfactants as low-adsorption surfactants for applications including, but not limited to, IOR, drilling, viscoelastic surfactants, acid treatment, crushing, foaming, and production, including, but not limited to, alkylamidopropyl betaine sulfonates, alkyldimethyl betaine sulfonates, alkylhydroxysultaine sulfonates, alkylsulfobetaine sulfonates, and alkylamine oxide sulfonates.

[0075] 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 one or more salts, such as monovalent and / or divalent inorganic salts.

[0076] In many of the formulations of the present invention, about 40% by weight of the disclosed aqueous hydraulic fracturing composition comprises a carrier (for example, the carrier is present in the composition in an amount ranging from at least about 40% by weight to about 99.88% by weight, e.g., 40%, 50%, 60%, 70%, 80%, 90%, 95% or more by weight). The carrier may be any suitable material capable of dissolving the active and auxiliary raw material components and delivering 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 may also be prepared as a gel, dip, foam, or spray.

[0077] 2. Alkaline Alkali are used, as is well known in the art, in some cases to form an "in situ" surfactant that acts synergistically with the injected surfactant. Examples of alkalis that may be used to practice the present invention include, but are not limited to, sodium hydroxide, sodium carbonate, sodium borate, and sodium silicate. Typically, alkali is used at a concentration of 0 to about 5% by weight of the injected fluid, but may be added further as needed.

[0078] 3. Viscosity-reducing agent Examples of viscosifiers that may be used to implement the present invention include, but are not limited to, polyacrylamide, AMPS copolymer, xanthan gum, other natural and synthetic gums, and polymers commonly known in the art and used to increase the viscosity of the injection fluid when control of mobility and flow efficiency is required. Generally, viscosifiers may be used as needed, but are typically used at a concentration of 0 to about 1% by weight of the injection fluid.

[0079] 4. Cosolvent As is well known in the industry, cosolvents can be used to reduce the viscosity of the injection fluid and improve its compatibility with freeze-thaw cycles or high concentrations. Exemplary cosolvents include, but are not limited to, C1-C8 alcohols, C1-C8 alcohol alkoxylates, and glycerin. The cosolvent is used at a concentration of 0 to about 50% by weight of the injection fluid.

[0080] 5. Surfactants and Co-surfactants Examples of surfactants and co-surfactants that can be used include one or more compounds selected from the group including anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. These are used by those skilled in the art. Generally, co-surfactants are used in concentrations of 0 to about 5% by weight of the total injected liquid formulation, but may be added further as needed.

[0081] The IOR fluid formulation of the present invention comprises one or more surfactants, also referred to as a surfactant system. The surfactant system may be used as a dispersant or a wetting agent. The surfactant system may also be used as an emulsifier component to form a stable emulsion. The emulsifier component may also be used to form a stable, emulsifiable concentrate. The surfactant system comprises at least one surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, or a nonionic surfactant, and optionally at least one other surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof.

[0082] Suitable surfactants used in the base fluid formulations of this disclosure are those of formula I or II

[0083] [ka]

[0084] [In the formula, R 1 and R 2The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12 The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. It contains one or more surfactants and / or copolymers.

[0085] Specifically, R 3 C2~C 10 Alkenyl, C2~C 10 Alkinyl, C2~C 12 Ester, C1~C 10 Hydroxyl, benzyl, C2-C 12 The second molecule of formula I may be selected from the group consisting of alkoxyalkyl ethers, alkyl phosphates, alkyl phosphonates, C3-C8 carboxylic acids, C1-C5 alkylbenzoic acids, and a 3-carbon linker bonded to the second molecule of formula I, wherein the second molecule of formula I is the same as the first molecule of formula I.

[0086] More specifically, R 3The following set of formulas may be selected.

[0087] [ka]

[0088] A suitable surfactant or co-surfactant may include one or more of the surfactants 1 to 12 described herein. The total amount of one or more surfactants in the base fluid formulation may be within the range of approximately 1% by weight or more, approximately 5% by weight or more, approximately 10% by weight or more, or approximately 15% by weight or less, approximately 20% by weight or less, approximately 25% by weight or less, approximately 30% by weight or less, approximately 35% by weight or less, or within the range of 1% to 35% by weight, or 5% to 35% by weight, or 10% to 30% by weight, or 15% to 20% by weight, or within any range using any two of the aforementioned values.

[0089] 6. Co-emulsifiers or co-surfactants Some embodiments of the present invention involve the use of foam-forming surfactant compositions comprising a mixture of these surfactants, blended with at least one surfactant according to the present disclosure, as well as at least one additional surfactant, e.g., a sulfosuccinate surfactant and at least one sulfosuccinate surfactant selected from monoester sulfosuccinate surfactants and diester sulfosuccinate surfactants, and a blend thereof, and further surfactants, in particular alkanolamides, alkyl sulfates, alpha-olefin sulfonates, betaines, fatty acid soaps, aliphatic alcohol alkoxylates, ethoxylated sorbitan esters, and sulfobetaines, to produce an increased amount of stable foam exhibiting an extended half-life in seawater, seawater / diesel mixtures, and brine. These surfactant mixtures may optionally contain a solvent, which is preferably water, or an aqueous solution also containing a salt, a foaming agent, e.g., xanthan gum, an oil which may be a hydrocarbon oil or vegetable oil, and a thickener or preservative. Compared to foam-forming compositions of the prior art, these formulations result in improvements in the amount of foam produced, foam stability, and foam persistence.

[0090] Some commercially desirable foaming surfactant compositions described herein exhibit improved foaming performance in a variety of aqueous media, including seawater (typically containing approximately 3.5% by mass fraction of dissolved salts, the majority of which is sodium chloride) and brine (i.e., aqueous salt solutions typically containing up to 12%, e.g., 0.1% to 11%, of monovalent and divalent cationic dissolved salts by mass fraction). The improved surfactant compositions function at ambient temperatures (typically 23°C) and lower temperatures, e.g., both between 1°C and 23°C, or at higher temperatures, e.g., above 23°C, up to 95°C. This involves the step of creating a formulation that increases the total volume of foam and improves foam stability and maximum foam lifetime (i.e., foam half-life, the time required to separate 50% of the volume of liquid medium from the original foam). Furthermore, the foam-forming surfactant compositions fully described herein are advantageous in that they exhibit improved performance at lower concentrations, thereby reducing exposure to the environment and workers, while simultaneously exhibiting a lower tendency to form oil-in-water emulsions, which is also advantageous as it simplifies oil recovery in production.

[0091] III. Emulsions and / or foams Aqueous foam-forming surfactant compositions can be prepared by adding water or a saline aqueous solution such as seawater or brine to a mixture with hydrocarbons, or to a mixture of hydrocarbons and one or more foam-forming surfactant compositions as described herein in an effective foam-forming amount. Supercritical gas may also be used as the liquid medium, to which foam-forming surfactant compositions as described herein in an effective foam-forming amount may be added. The types of surfactants detailed in the present invention include anionic surfactants, mixtures of two or more anionic surfactants, and any combination thereof having cationic, amphoteric, zwitter, and nonionic surfactants, and the gas may include, for example, one or more air, carbon dioxide, nitrogen, methane, or other natural and generated gases.

[0092] One method for improving oil recovery from wells is the miscible gas method. The miscible gas method, using carbon dioxide, can reduce the viscosity of crude oil present in the subsurface to increase the flow of hydrocarbons into production wells. Acting as a solvent to reduce the viscosity of crude oil, carbon dioxide is an effective and relatively inexpensive miscible gas. During the procedure of the miscible carbon dioxide method, carbon dioxide is typically in a liquid and / or supercritical phase. A method used to increase the effectiveness of the miscible gas method is to add foaming surfactants to the process.

[0093] One aspect of the present invention includes a method for recovering petroleum or natural gas from a reservoir or subsurface oil- or gas-containing geological formation during gas injection using a foam-forming surfactant composition. The method envisioned by the present invention includes the step of bringing oil or gas in the formation into contact with one or more of the foam-forming surfactant composition and the injected gas to assist in oil recovery. The method envisioned herein for the recovery of petroleum or natural gas using the foam-forming surfactant composition described herein can be carried out as part of one or more of the industry standard primary, secondary, or tertiary recovery techniques.

[0094] The foam-forming surfactant compositions of the present invention can be used as a solvent or a solution in a liquid vehicle, the solvent being selected from water, aqueous saline solutions, liquefied gases, supercritical gases, and mixtures thereof. Typically, the surfactant is incorporated into an aqueous medium to produce foam. When an aqueous saline solution is used as the solvent, an aqueous foam-forming surfactant composition is obtained, and the combination of the foam-forming surfactant composition with water or an aqueous saline solution preferably contains at least 0.2%, preferably up to 10%, of dissolved inorganic salts by mass fraction, from which foam can be produced by closely mixing with gas in a foam generator. Foam can also be produced in situ through introduction into subsurface oil- or gaseous geological structures containing, in many cases, water or an aqueous saline solution, under pressure, the gas and alternative slag of the foam-forming surfactant composition. At least 0.2%, preferably up to 10%, of dissolved inorganic salts by mass fraction is typically obtained therefrom.

[0095] In the recovery of hydrocarbons such as oil and natural gas, the role played by emulsions includes, for example, foam which can be used to enhance the recovery of gas or oil from a well source. In some embodiments, the emulsion may be formed using oil or gas recovered, for example, from a well or from a bioprocess product. In some embodiments, the surfactants of the present invention disclosed herein are used to create the emulsion, for example, foam. In yet other embodiments, the surfactant may be used to break down the emulsion containing the recovered oil or gas.

[0096] Foam can be formed by adding an effective amount of at least one anionic surfactant present in an effective amount of a high-salinity foaming fluid composition that generates an interfacial tension (IFT) of only 10-mN / m. The anionic surfactant may be the surfactant of the invention, or a sulfonate surfactant and / or a sulfate surfactant. The foaming fluid composition may be used to perform operations including, but not limited to, gas lift operations, drilling operations, finishing operations, agitation operations, crushing operations, injection operations, enhanced oil recovery operations, and combinations thereof.

[0097] Foaming fluids are used in a variety of applications during the recovery of hydrocarbons from underground reservoirs. Foaming fluids include a base fluid, a foaming agent, and a fluid containing gases, including but not limited to nitrogen, carbon dioxide, air, and methane. The base fluid can be foamed to reduce the amount of base fluid required, reduce the amount of fluid loss to the formation, and / or enhance the propane suspension in the fracturing fluid. "Foaming agent" is defined herein as an agent that promotes foaming of the base fluid when mixed with a gas.

[0098] The foaming fluid can also be used during stimulation operations (e.g., unloaded gas wells) to replace any existing fluids and / or formation fluids present in the well. “Existing fluids” is defined herein as the fluids present in the subsurface reservoir well before the foaming additive and / or foaming fluid composition is introduced into the subsurface reservoir well. “Formation fluids” is defined herein as any fluid generated from oily subsurface formations, including but not limited to oil, natural gas, and water. While formation fluids are considered existing fluids, existing fluids are not necessarily formation fluids. For example, other fluids in the well may be injected into the subsurface reservoir well and remain present in the well even when the foaming additive is introduced. Therefore, fluids in the well (e.g., drilling fluid, finishing fluid, fracturing fluid, injection fluid, etc.) can be “base fluids” when introducing the foaming additive and gas into the subsurface reservoir well.

[0099] The base fluid of the foaming fluid may be a drilling fluid, finishing fluid, stimulating fluid, fracturing fluid, injection fluid, or a combination thereof. Non-limiting examples of the use of such fluids may be in conjunction with unloaded oil or gas wells, enhanced oil recovery operations, heavy oil recovery, drilling operations, fracturing operations, pressure pumping, cement solidification, acid treatment or other stimulating operations, etc.

[0100] An example of a foamed drilling fluid, though not limited to this, may be when drilling operations require a drilling fluid with a low density, for example, a foamed drilling fluid with a density of approximately 2.0 ppg (approximately 0.24 g / cm³). 3 ) to approximately 8.0 ppg (approximately 0.96 g / cm³) 3 It may also be within the range of ).

[0101] Drilling fluids are typically classified according to their base fluid. In water-based fluids, 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 all be water or brine, an oil-in-water emulsion, or an oil-in-brine emulsion. A brine-based fluid is, of course, a water-based fluid, where the aqueous component is water-based. An oil-based fluid is the opposite or reverse of a water-based fluid.

[0102] "Oil-based fluid" is used herein to include fluids having a non-aqueous continuous phase, where the non-aqueous continuous phase is all oils, non-aqueous fluids, water-in-oil emulsions, water-in-aqueous-water emulsions, brine-in-oil emulsions, or brine-in-aqueous-water emulsions. In oil-based fluids, 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, oil may consist of any oil or fluid immiscible with water, but is not limited to diesel, mineral oil, esters, refinery cuts and blends, or α-olefins. Oil-based fluids as defined herein may also include synthetic base fluids or slurry (SBM) which are produced synthetically rather than refined from naturally occurring materials. Synthetic base fluids often include, but are not limited to, ethylene olefin oligomers, 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, and mixtures of these types of brines.

[0103] One type of drilling operation involves cement solidification, where cement is delivered to a location within the well. Cement solidification can be used to seal annular sections after a casing string has passed through, to seal areas of lost circulation, to set plugs in existing wells and push them out with directional tools, or to fill wells with plugs so that they can be abandoned. Before commencing cement solidification, the required volume of cement to be placed in the well, as well as the physical properties of the slurry and cement to be set, including density and viscosity, are determined. Drilling fluid may be replaced to place the cement in the well. When performing primary cement solidification and repair cement solidification operations in a well, the cement slurry used must often be lightweight to prevent excessive hydrostatic pressure in the subsurface formation through which the well penetrates. As a result, a variety of lightweight cement slurries, including foamed cement slurries, have been developed and are in use.

[0104] In addition to being lightweight, foamed cement slurry contains compressed gas, improving the slurry' ability to maintain pressure and its ability to prevent the flow of formation fluid into and through the slurry during its transition time, i.e., the time it takes for the cement slurry to change from a complete fluid to a solidified mass. Other surfactants, in addition to those used as foaming agents, may be used as foam stabilizers to prevent premature separation of the foam slurry into slurry and gaseous components, and may also be added to the slurry. Foamed cement slurry may have the property of low fluid loss.

[0105] A variety of functions and properties are expected for finishing fluids. Finishing fluids may be added to wells to facilitate the final work before production begins. Finishing fluids are typically brines containing chlorides, bromides, and formates, but may be any harmless fluid with appropriate density and flow properties. Suitable salts for forming brine include, but are not 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 finishing fluid with the reservoir formation and fluid can be extremely important. Chemical additives such as polymers and surfactants are known in the industry to be introduced into brines used in well servicing fluids for a variety of reasons, including, but not limited to, increased viscosity and increased brine density.

[0106] Service fluids, such as repair fluids, stimulating fluids, and refurbishment fluids, possess several functions and properties necessary for the repair of damaged wells. Such fluids may be used to break down already formed emulsions, as well as to remove formation damage that may have occurred during drilling, finishing, and / or production operations. The terms “repair work” and “repair” are defined herein as including the reduction of viscosity of damaged gels, and / or the partial or complete removal of any type of damage from subsurface formations. Similarly, the term “repair fluid” is defined herein as including any fluid that may be useful in repair work. Stimulating fluids are treatment fluids prepared to stimulate, restore, or enhance the productivity of a well, such as, in some but not limited examples, fracturing fluids and / or matrix stimulating fluids.

[0107] Hydraulic fracturing is a type of stimulation operation that uses pump speeds and water pressure to fracture or crack subsurface formations in order to improve the recovery of hydrocarbons from geological formations. Once a crack(s) are formed, propane with a higher permeability than the formation's permeability is pumped into the fracturing area, supporting the opening of the crack. When the applied pump speed and pressure are reduced or removed from the formation, the crack or fracturing area cannot be completely closed or repaired because the high-permeability propane holds the crack open. The supported crack or fracturing area provides a high-permeability pathway 40, which increases the formation area of ​​the well and leads to increased hydrocarbon production.

[0108] Another type of stimulation operation is when an oil or gas well is "unloaded." In most gas wells, water and / or condensates are produced along with the gas. In mature gas wells, as the formation pressure and gas flow velocity gradually decrease, the well becomes "loaded" with liquid. Because dealing with liquid-loaded wells with a large amount of condensate cuts is difficult, operators can use various methods to prevent liquid loading in critical gas wells.

[0109] No-load operation of oil or gas wells may be necessary if primary production techniques (i.e., using only initial geological energy to recover crude oil), followed by secondary techniques such as watering, recover only a small percentage of the original reserves present in the formation. Average recovery rates after secondary recovery operations are approximately 25-35% for oil fields and approximately 70% for gas fields. Gas and oil well production systems are generally limited in production due to oil and water loads in the passages.

[0110] Gas lifting and / or deliquification of wells can allow wells with liquid load problems to return to a state of continuous flow, increase flow in currently productive wells, restart wells, and a combination of these. Typically, since oil and / or gas are produced from the reservoir, the pressure in the reservoir formation decreases, and production declines. Furthermore, due to finishing problems, well production may decline over long periods, making it difficult to restart the well. A method commonly used to deliquify, or "unload," these wells is by applying chemical blowing agents.

[0111] The use of foam generated in situ by the injection of surfactant-modified gas (SAG) is described in RF 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, as an alternative to polymers working in alkaline / surfactant / polymer (ASP) enhanced oil recovery (EOR) processes.

[0112] Micelle-based alkaline soapy substances may be used to reduce the interfacial tension between oil and water in the reservoir and to give mobility to the oil present in the reservoir, while polymers such as polyacrylamide or polysaccharides may be used to improve the flow efficiency, which is a measure of the effectiveness of EOR operations that depends on the mobility ratio and the volume of the reservoir in contact with the injected fluid.

[0113] In non-limiting alternative embodiments of the method, the method may include the step of unloading an oil or gas well in an oil-bearing subsurface formation by introducing a foaming fluid composition into the subsurface reservoir well containing an existing fluid. The foaming fluid composition may have, or may contain, 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 C20-C24 carbon chains and internal olefins. The foaming fluid composition has a salt content 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 subsurface reservoir well.

[0114] Further provided are other forms of foaming fluid compositions having a base fluid, a gas, at least one anionic surfactant, and at least one second surfactant. The base fluid may be an oil-based fluid, an aqueous-based fluid, or a combination 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 an effective amount in the foaming fluid composition to obtain an IFT of about 10⁻¹ mN / m to about 10⁻³ mN / m. The at least one second surfactant includes, but is not limited to, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and combinations thereof. The foaming fluid composition has a salt content of 30,000 total dissolved solids (TDS) or more.

[0115] In another non-limiting embodiment of the foaming fluid composition, the anionic sulfonate surfactant(s) may have or contain C20-C24 carbon chains and internal olefins therein, and the amount of at least one anionic surfactant is in the range of about 1 vol% to about 50 vol% based on the total foaming fluid composition.

[0116] In one embodiment, a method is provided which may include the step of performing work with a foaming fluid composition. The foaming fluid composition may have, or may contain, a base fluid, a gas, and at least one anionic surfactant having a hydrophobic chain of at least 20 carbon atoms, the anionic surfactant being selected from the group consisting of sulfonates.

[0117] 1. Surfactants Suitable surfactants used in the formulations of the inventions disclosed herein are those of formula I or II

[0118] [ka]

[0119] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. It contains one or more surfactants and / or copolymers.

[0120] Specifically, R 3 C2~C 10 Alkenyl, C2~C 10 Alkinyl, C2~C 12 Ester, C1~C 10 Hydroxyl, benzyl, C2-C 12 The second molecule of formula I may be selected from the group consisting of alkoxyalkyl ethers, alkyl phosphates, alkyl phosphonates, C3-C8 carboxylic acids, C1-C5 alkylbenzoic acids, and a 3-carbon linker bonded to the second molecule of formula I, wherein the second molecule of formula I is the same as the first molecule of formula I.

[0121] More specifically, R 3 The following formulas may be selected from the group.

[0122] [ka]

[0123] A suitable surfactant or co-surfactant may contain one or more of the surfactants 1 to 12 described herein. 2. Second surfactant At least one anionic surfactant has a hydrophobic chain of 12 to 24 carbon atoms, and 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.

[0124] 3. Base fluid The base fluid may be an oil-based or water-based fluid selected from the group consisting of drilling fluids, finishing fluids, stimulating fluids, fracturing fluids, gas well deliquescing fluids, coiled tubing working fluids, recycling drilling fluids, service fluids, well cleanout fluids, well intervention fluids, capillary coiled tubing fluids, and combinations thereof.

[0125] 4. Gas Any suitable gas may be mixed with any liquid or combination of liquids in any suitable formulation to form an emulsion containing bubbles and / or air. Gases that may be used include, but are not limited to, air, nitrogen, carbon dioxide, natural gas, and any combination thereof.

[0126] IV. Fluids for recovering bio-oil Bio-based oils, including edible oils from naturally occurring sources, are essential for human nutrition and, until relatively recently, have also been a source of light and even energy. Naturally occurring sources of oil include seeds and fruits, some of which are cultivated primarily as oil sources. Sources of bio-based oils that may be used in fuels, including biodiesel fuel, include naturally occurring soybeans and bio-engineered algae. Any formulations and / or processes that can be used to increase recovery and / or improve the quality of recovered oil are beneficial.

[0127] Other sources of bio-based oils include distillation wastewater 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 the extraction of emulsified oil from an oil-water emulsion. The composition may 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 may also include silicon-containing particles. Several methods for recovering oil from a corn ethanol process are also provided. These methods may include the steps of adding the composition to a process stream of a corn ethanol process and extracting the oil from the process stream.

[0128] The formulation for recovering edible oil contains only reagents that are generally considered safe (GRAS) by regulatory authorities such as the U.S. Department of Agriculture and the U.S. Food and Drug Administration. Sources of bio-based oils that may be used in fuels, including biodiesel fuel, include naturally occurring soybeans and bio-engineered algae.

[0129] Most commercial corn oil is produced by tip fractionation of the corn germ during the wet milling process of corn. Recently, a new source of corn oil has emerged as a byproduct of the dry milling process used in the ethanol industry. Dry milling requires less energy and capital investment than wet milling. While the corn oil captured at the end of the dry milling process is not suitable for food use, it can be used as a raw material for biodiesel.

[0130] 1 Aqueous component The aqueous component may include, for example, fresh water or seawater, and most commonly, the aqueous phase contains water containing one or more inorganic salts.

[0131] 2. Supercritical gas Some inventions involve supercritical gases, such as carbon dioxide. Supercritical carbon dioxide (CO2) is a fluid state of gas where the gas is held at or above its critical temperature and critical pressure. In this state, the gas exhibits some properties that are intermediate gases and liquids. Supercritical carbon dioxide exists at temperatures of approximately 31.1°C or above, and pressures above approximately 7.39 MPa.

[0132] 3. Surfactants Suitable surfactants used in the invention formulations of this disclosure are those of formula I or II

[0133] [ka]

[0134] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12 The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. It contains one or more surfactants and / or cosurfactants.

[0135] Specifically, R 3 may be C2 - C 10 alkenyl, C2 - C 10 alkynyl, C2 - C 12 ester, C1 - C 10 hydroxyl, benzyl, C2 - C 12 alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3 - C8 carboxylic acid, C1 - C5 alkyl benzoic acid, and a 3 - carbon linker bonded to the second molecule of Formula I, and the second molecule of Formula I is the same as the first molecule of Formula I.

[0136] More specifically, R 3 may be selected from the group consisting of the following formulas.

[0137]

Chemical formula

[0138] Suitable surfactants or cosurfactants may include any one or more of Surfactants 1 - 12 described herein. The aforementioned surfactant can be combined with other surfactants including, for example, a sulfosuccinate - type surface of the formula: R - NX - CO - CHY 1 - CHY 2 - CO - O - M 4+ wherein Y

[0139] [In the formula, Y 1 is H, Y 2 is (SO3M 3+ ), or Y 1 is (SO3M 3+ ), and Y 2 is H. 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 linear or branched or cyclic aliphatic radical having 8 to 24 carbon atoms, optionally one or more carbon-carbon double bonds, or a mixture of two or more such radicals. X may be a hydrogen atom or an alkyl carboxylate group --(CRR)-COOM 2+ , where both R' and R may be H, or R may be H and R may be -CH COOM 3+ , and M 3+ and M + are cations, which may be the same or different, and are 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. M 3+ , M + , M 2+ and M 4+ Particularly preferred alkali metal ions as are, independently of each other, sodium cation, Na + , and potassium cation, K + .

[0140] Further surfactants optionally included in the indicated separation aid compositions may be, for example, nonionic surfactants, cationic surfactants, or anionic surfactants. The surfactant(s) may be one or more nonionic surfactants, such as ethoxylated castor oil, ethoxylated sorbitan esters, PEG, poloxamer, acetylene glycol or sulfonates, or combinations thereof. Nonionic surfactants may be, for example, nonionic polyethylene glycol, such as ethoxylates of carboxylic acids, mono-, di- or triglycerides, 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 aids of the present invention include, for example, Lumisorb Polysorbates (Gurnee, Ill. USA) from Lambent Technologies Corporation. The nonionic surfactant may be at least one poloxamer. The poloxamer may be a nonionic triblock copolymer comprising a central block of hydrophobic polyalkylene oxide blocks flanked on both sides by hydrophilic polyalkylene oxide blocks. Poloxamers are commercially available in food grade. A commercial source of poloxamers is, for example, PLURONIC® copolymer from BASF Corporation (Florham Park, NJ, USA).

[0141] The water solubility of surfactants, such as nonionic surfactants, may be related to their hydrophilic-lipophilic balance (HLB) value or number. Nonionic surfactants can have HLB values ​​of at least about 6, or at least about 9, or at least about 12, or about 6 to 20, or about 7 to about 19, or about 8 to about 18, or about 9 to about 17, or about 10 to about 16, or other values. The water solubility of nonionic surfactants may be related to their hydrophilic-lipophilic balance (HLB) value or number. HLB values ​​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 has an HLB value calculated as 16 (i.e., 80 / 5 - 16). HLB values ​​greater than 20 are relative or comparative values.

[0142] Some of the inventive formulations may contain one or more surfactants in amounts ranging from about 0% by weight or more, about 2% by weight or more, about 4% by weight or more, about 6% by weight or more, about 8% by weight or more, or about 10% by weight or less, about 12% by weight or less, about 14% by weight or less, about 16% by weight or less, or any of these endpoints.

[0143] 4. Oil Oils that may be used to put the present invention into practice 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.

[0144] The oils contained in the separation aids shown may be, for example, mineral oils, triglyceride vegetable oils, hydrocarbon oils, or any combination thereof. Mineral oils may be, for example, white mineral oils or mineral seal oils. Examples of mineral oils may be atmospheric residue oils obtained from the distillation of crude oil, vacuum diesel oils, and vacuum residue oils obtained from the vacuum distillation of atmospheric residue oils, their hydrotreated oils, pyrolysis oils, and / or mixtures thereof. Of these mineral oils, atmospheric residue oils, vacuum residue oils, and their hydrolyzed or pyrolysis products are referred to as residue oils in this invention. Triglyceride vegetable oils may be, for example, triglyceride corn oil. Hydrocarbon oils may be, for example, white mineral oils or any combination thereof. Commercial sources of oils that can be used in the separation aids of this invention include, for example, Clarion White Mineral Oil 70 and CITGO Petroleum (Houston, USA).

[0145] 5. Lecithin Lecithin used as a separation aid may be of natural origin, modified origin, or synthetic. Lecithin that can be used in the present invention may be lecithin derived from any plant, animal, or microbial source. Suitable lecithin starting materials include commercially available soy lecithin and egg yolk lecithin products. Lecithin is obtained from natural sources, such as egg yolk, and from plants, such as soybeans, maize, and rapeseed, which are byproducts of vegetable oil refining. Soybean oil is the largest source of commercial lecithin. The composition of commercial lecithin depends on the source, method of preparation, and degree of refining, 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, accompanied in small amounts by other components 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 contains phosphatidylcholine and phosphatidylethanolamine as its main phospholipids. Lecithin can be extracted chemically (using hexane) or mechanically from readily available sources, such as soybeans. Lecithin has low solubility in water. In aqueous solution, its phospholipids can form liposomes, bilayer sheets, micelles, or lamellar structures depending on hydration and temperature. This produces materials of a type usually classified as amphiphilic. As used herein, "modified lecithin" refers to, but is not limited to, acetylation, hydroxylation, hydrogenation, hydrolysis products, chlorination, bromination, iodization, halogenation, phosphorylation, and sulfonation of lecithin, as well as other modifications known to those skilled in the art. Acetylated lecithin can be produced using carboxylic acid anhydrides, such as acetic anhydride for acetylation of phospholipids from plant lecithin, for example, as shown in U.S. Patent No. 3,301,881, which is incorporated herein by reference in whole.The enzymatic process can be used to prepare acetylated phospholipids 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 by using vinyl acetate as an acylating agent in the presence of lipase from Mucor Miehei, which has 1,3-position specificity, for example, as shown in U.S. Patent No. 6,403,344, which is incorporated herein by reference in whole. In acetylated lecithins, for example, acetylation occurs mainly at the amino group of phosphatidylethanolamine. The degree of acetylation in denatured lecithins may be partial or complete, depending on the application. The degree of acetylation in denatured lecithin may be, for example, about 5% to 100%, or about 10% to 99%, or about 15% to 95%, or about 20% to 90%, or about 25% to 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, phosphonic acid esters, amines, and hydroxyl groups. Denaturation can also result in transesterified lecithin. Furthermore, lecithin can be a denatured enzyme. As used herein, "phosphatide" (phospholipid) refers to, but is not limited to, mixtures of phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, phosphatidic acid, N-acylphosphatidylethanolamine, and other related fewer components. Commercial sources of lecithin or denatured lecithin that can be used in the separation aid of the present invention include, for example, Solec HR2B from Solae LLC (Memphis, Tenn. USA).

[0146] 6. Silica For example, separation aids may contain silica, such as fumed silica. Fumed silica can be hydrophobic or hydrophilic. Fumed silica is food-grade, which may be preferable for this reason. Condensed fumed silica can be included in the separation aid in amounts of, for example, about 1% to 10% by weight.

[0147] 7. Water-insoluble solvents and oils Suitable water-insoluble, immiscible organic solvents include natural, non-petroleum sources, such as those derived from or made from plants and animals, and also include vegetable oils, seed oils, animal oils, etc., as well as such N,N-dimethylcaprylamide (N,N-dimethyloctanamide), N,N-dimethylcapramide (N,N-dimethyldecanamide) and mixtures thereof, which are commercially available as Agnique® AMD 810 and Agnique® AMD 10 from BASF Corp. (Florham Park, NJ), Genegen® 4166, Genegen® 4231 and Genegen® 4296 from Clariant (Charlotte, NC), 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 caprylic / capric acid fatty acid (C8 / C10) morpholinamide, which is commercially available as JEFFSOL® AG-1730 solvent from Huntsman International LLC (The Woodlands, Tex.).

[0148] Other suitable water-insoluble solvents may include aromatic hydrocarbons, mixed naphthalene and alkylnaphthalene fractions, aromatic solvents, particularly alkyl-substituted benzenes, such as xylene or propylbenzene fractions; C1-C6 esters of fatty acids derived from plant, 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; ketones, such as isophorone and trimethylcyclohexanone (dihydroisophorone); acetate esters, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate or heptyl acetate; and cyclic alkyl carbonates, such as propylene carbonate and butylene carbonate, which can be used as JEFFSOL® alkylene carbonate from Huntsman (The Woodlands, Tex.), also from Huntsman, and dibutyl carbonate; and mixtures of any of the water-immiscible organic solvents described herein.

[0149] The water-insoluble solvent may be present in amounts of approximately 0% by weight or more, approximately 10% by weight or more, approximately 20% by weight or more, or approximately 30% by weight or less, approximately 40% by weight or less, approximately 50% by weight or less, or any of these endpoints.

[0150] 8. Water Water can be present in the formulations of the Disclosure and can serve as both an aqueous solvent and a carrier for the raw material components in the compositions described. Some formulations of the Disclosure may contain water in amounts 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 any of these endpoints.

[0151] 9. Other additives The formulations of the present invention may contain one or more additional suitable raw material components. These additional raw material components may include, for example, one or more solvents or other raw material components, which may be dissolved or dispersed in the composition, and may be selected from acaricides, algicides, birdicides, fungicides, bird repellents, and sterilizers. In addition, any other additional raw material components with functional utility, such as defoamers, antimicrobial agents, buffers, corrosion inhibitors, dispersants, freezing point depressants, neutralizing agents, odorants, penetration aids, metal ion chelating agents, stabilizers, binders, viscosity modifiers, etc., may be included in these compositions.

[0152] When the formulation is used in combination with additional active ingredients, for example, the compositions described herein may be formulated with other active ingredients as other active ingredients or as a premix concentrate, and may be tank-mixed with other active ingredients in water.

[0153] 10. Manufacturing Method The formulations disclosed herein include: 1) preparing a solution in an organic solvent and a surfactant; 2) Add the solution prepared in step 1) to a concentrated solution of water-soluble salts in water while mixing thoroughly to form a clear solution; Furthermore, 3) it may be prepared by optionally adding any additional suitable active or inactive component.

[0154] Alternatively, the formulations of the present disclosure may be prepared by: 1) preparing an oil and optionally mixing it with an organic solvent and a surfactant; 2) 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 adding any additional suitable active or inactive component.

[0155] Suitable water-compatible raw material components that may be added to the formulation include, but are not limited to, water-soluble or water-insoluble dispersible surfactants, such as the surfactants of this disclosure, water-insoluble active ingredients, and optionally other inert components, such as pH buffers, wetting agents, antifreezes, defoamers, and biocides.

[0156] 11. How to use The solution may be added to a naturally occurring source of oil, such as soybean mash or algal biomass, or to a synthetic source of oil, such as distillation wastewater from a maize ethanol production process. Once mixed with the 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, or freezing.

[0157] 12. Surfactants The foaming compound may contain one or more surfactants selected from one or more surfactant classes, and is collectively referred to as a surfactant system.

[0158] This disclosure provides surfactants in the form of amino acid siloxane derivatives for use in oil and gas production. Accordingly, the use of compounds of formula I or II as surfactants in oil and gas production is disclosed herein.

[0159] Suitable surfactants used in the formulations of this disclosure are those of formula I or II

[0160] [ka]

[0161] [In the formula, R 1 and R 2 The groups may be the same or different, and each group comprises at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid and additional surfactant molecules having the structure represented by formula I are bonded to C1-C12. 12 The group consisting of linkers may be selected, where the additional surfactant molecule of formula I may be the same as or different from the surfactant molecule of formula I; n and z may be independently chosen from any integer between 1 and 12; m can be any integer between 1 and 12; X may be selected from the group consisting of chloride, bromide, and iodide. It contains one or more surfactants and / or copolymers.

[0162] Specifically, R 3 C2~C 10 Alkenyl, C2~C 10 Alkinyl, C2~C 12 Ester, C1~C 10 Hydroxyl, benzyl, C2-C 12 The second molecule of formula I may be selected from the group consisting of alkoxyalkyl ethers, alkyl phosphates, alkyl phosphonates, C3-C8 carboxylic acids, C1-C5 alkylbenzoic acids, and a 3-carbon linker bonded to the second molecule of formula I, wherein the second molecule of formula I is the same as the first molecule of formula I.

[0163] More specifically, R 3 The following set of formulas may be selected.

[0164] [ka]

[0165] In particular, a suitable surfactant or co-surfactant may contain one or more of the surfactants 1 to 12 described herein. Further compounds provided by this disclosure are those compounds of formula I, wherein R1 and R2 are methyl.

[0166] Other compounds provided by this disclosure are compounds of formula I, where n and / or z are 5. As used herein, the phrase "n may be an integer from 1 to 12" means that n may be equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12.

[0167] As used herein, the term "C1-C6 alkyl" means a linear or branched alkyl group containing 1, 2, 3, 4, 5, and / or 6 carbon atoms. As used herein, the term "C1-C6 linker" means a linear or branched alkyl chain containing 1, 2, 3, 4, 5, and / or 6 carbon atoms.

[0168] As used herein, the term "C2-C10 alkenyl" means a linear or branched alkenyl group containing 2, 3, 4, 5, 6, 7, 8, 9 and / or 10 carbon atoms.

[0169] As used herein, the term "C2-C10 alkynyl" means a linear or branched alkynyl group containing 2, 3, 4, 5, 6, 7, 8, 9 and / or 10 carbon atoms.

[0170] As used herein, the term "C2-C12 ester" means a linear or branched ester group having a total of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 carbon atoms.

[0171] As used herein, the term "C2-C12 alkoxyalkyl ether" means a linear or branched alkoxyalkyl ether group having a total of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12 carbon atoms.

[0172] As used herein, the phrase "C1-C10 hydroxyl" means a hydroxyl group bonded to a linear or branched alkyl group containing 1, 2, 3, 4, 5, 6, 7, 8, 9 and / or 10 carbons.

[0173] As used herein, the phrase "C3-C8 carboxylic acid" means a carboxylic acid group bonded to a linear or branched alkyl group containing 3, 4, 5, 6, 7 and / or 8 carbons.

[0174] As used herein, the phrase "C1-C10 alkyl benzoic acid" means a benzoic acid group bonded to a linear or branched alkyl group containing 1, 2, 3, 4, 5, 6, 7, 8, 9 and / or 10 carbons.

[0175] As used herein, the phrase "n and z may be independently selected from any integer from 1 to 12" means that n and z may independently be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12.

[0176] As used herein, the phrase "m may be any integer from 1 to 12" means that m may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and / or 12.

[0177] As used herein, the phrase "q may be any integer from 1 to 10" means that q may be 1, 2, 3, 4, 5, 6, 7, 8, 9 and / or 10.

[0178] One specific compound provided by this disclosure and referred to herein as surfactant 1 is N-benzyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propylamino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the following formula:

[0179] [ka]

[0180] The second specific compound provided by this disclosure and referred to herein as surfactant 2 is N-(2-ethoxy-2-oxoethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the following formula:

[0181] [ka]

[0182] A third specific compound provided by this disclosure and referred to herein as surfactant 3 is N-allyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium iodide having the following formula:

[0183] [ka]

[0184] The fourth specific compound provided by the present disclosure and referred to herein as surfactant 4 is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxo-N-(prop-2-yn-1-yl)hexan-1-aminium bromide having the following formula.

[0185] [Chemical formula]

[0186] The fifth specific compound provided by the present disclosure and referred to herein as surfactant 5 is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexan-1-aminium bromide having the following formula.

[0187] [Chemical formula]

[0188] The sixth specific compound provided by the present disclosure and referred to herein as surfactant 6 is N-(3-(diethoxyphosphoryl)propyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-aminium bromide having the following formula.

[0189] [Chemical formula]

[0190] The seventh specific compound provided by this disclosure and referred to herein as surfactant 7 is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexane-1-aminium iodide having the following formula:

[0191] [ka]

[0192] The eighth specific compound provided by this disclosure and referred to herein as surfactant 8 is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexane-1-aminium iodide having the following formula:

[0193] [ka]

[0194] The ninth specific compound provided by this disclosure and referred to herein as surfactant 9 is N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the following formula:

[0195] [ka]

[0196] A tenth specific compound provided in this disclosure and referred to herein as surfactant 10 is an N compound having the following formula: 1 ,N 3-Bis(6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)-N 1 ,N 1 ,N 3 ,N 3 It is tetramethylpropane-1,3-diaminium dibromide.

[0197] [ka]

[0198] A further group of specific compounds provided herein and referred to herein as surfactants 11-12 are general formulas:

[0199] [ka]

[0200] [In the formula, q may be an integer between 1 and 10.] It holds. The 11th specific compound provided by this disclosure and referred to herein as surfactant 11 is N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the following formula:

[0201] [ka]

[0202] The twelfth specific compound provided by this disclosure and referred to herein as surfactant 12 is N-(4-carboxybenzyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide having the following formula:

[0203] [ka]

[0204] These compounds can be synthesized by various methods. One such method involves reacting an amino acid, such as an N-alkylated or N-acylated amino acid, with a siloxane to convert the C-terminus of the amino acid into a desired siloxane derivative. The N-terminus of the amino acid may be further alkylated to obtain, for example, a quaternary amine.

[0205] The amino acids may be natural or synthetic, or they may be derived from the ring-opening reaction of lactams such as caprolactam. The ring-opening reaction may be acid-catalyzed or alkali-catalyzed, and an example of an acid-catalyzed reaction is shown in Scheme 1 below.

[0206] [ka]

[0207] An amino acid may have at least one or as many as twelve carbon atoms between its N-terminus and C-terminus, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. The alkyl chain may be branched or linear. The alkyl chain may contain nitrogen, oxygen, or sulfur atoms. The alkyl chain may further be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen may be acylated or alkylated with one or more alkyl groups. For example, the amino acid may be 6-(dimethylamino)hexanoic acid.

[0208] The siloxane may be substituted with one or more alkoxy groups such as methoxy, ethoxy, isopropoxy, or tert-butoxy. The siloxane may be further substituted with one or more alkyl groups such as propyl, in which case the alkyl group may be further substituted with a suitable functional group that enables coupling of the siloxane to an amino acid, such as nitrogen. For example, the siloxane may be 3-aminopropyltris(trimethylsiloxy)silane.

[0209] The siloxane derivatives of amino acids may be synthesized as shown in Scheme 2 below. As shown therein, 6-aminohexanoic acid is alkylated at its N-terminus by treatment with formaldehyde in formic acid under reflux to obtain 6-(dimethylamino)hexanoic acid. This free carboxylic acid is then coupled to 3-aminopropyl(trismethylsiloxy)silane in refluxed toluene to obtain the desired siloxane derivative.

[0210] [ka]

[0211] The N-terminal nitrogen may be further derivatized to modify or improve water solubility and surface activity properties. A sample synthesis scheme is shown in Scheme 3 below, in which case the N-terminal nitrogen is alkylated to obtain a quaternary amine.

[0212] [ka]

[0213] Suitable alkylating agents may include, for example, benzyl bromide, ethyl bromo, allyl iodide, propargyl bromide, 1-bromo-2-(2-methoxyethoxy)ethane, bromophosphonate, 3-iodopropanol, 3-bromopropanol, 2-iodoethanol, 2-bromoethanol, 6-bromohexanoic acid, 4-(4-bromobutyl)benzoic acid, and 4-(bromomethyl)benzoic acid. Two molecules of formula I may be linked by treating the N-terminal nitrogen with a bifunctional alkylating agent such as 1,3-dibromopropane.

[0214] The compounds disclosed herein exhibit surface-active properties. These properties can be measured and described by various methods. One way to describe surfactants is by the critical micelle concentration (CMC) of the molecule. CMC may be defined as the concentration of surfactant that forms micelles, at concentrations higher than this, all additional surfactant is incorporated into the micelles.

[0215] 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, and thus the minimum surface tension. Adding more surfactant does not further affect the surface tension. Therefore, the CMC can be measured by observing the change in surface tension as a function of surfactant concentration. One such method for measuring this value is the Wilhelmie plate method. A Wilhelmie plate is typically a thin iridium-platinum plate attached to a balance by wire and positioned perpendicular to the air-liquid interface. Using the balance, the force acting on the plate due to wetting is measured. Then, using this value, the surface tension (γ) is calculated according to Equation 1: Equation 1: γ = F / l cosθ In the formula, l is equal to the wet perimeter (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 there are no existing literature values.

[0216] Another parameter used to evaluate the performance of surfactants is dynamic surface tension. Dynamic surface tension is the value of surface tension over time at a particular surface or interface. In the case of a liquid to which a surfactant has been added, this can differ from the equilibrium value. Immediately after the surface is formed, the surface tension is equal to that of the pure liquid. As mentioned above, surfactants decrease the surface tension, so the surface tension decreases until it reaches the equilibrium value. The time required to reach equilibrium depends on the diffusion rate and adsorption rate of the surfactant.

[0217] One method for measuring dynamic surface tension is using a bubble-type tension meter. 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 specific surface elapsed time, which is the time from the start of bubble formation until the maximum pressure is reached. The dependence of surface tension on surface elapsed time can be measured by varying the rate at which bubbles are formed.

[0218] Surface-active compounds can also be evaluated by their wetting ability on solid substrates, measured by the contact angle. When a droplet comes into contact with a solid surface in a third medium such as air, a three-phase line is formed between the liquid, gas, and solid. The contact angle is described as the angle between the surface and the unit vector of surface tension, which plays a role in the three-phase line and is tangent to the droplet. The contact angle (also known as the wetting angle) is a measure of how well a liquid wets a solid. In the case of complete wetting, the liquid spreads completely over the solid, and the contact angle is 0°. Wetting properties are typically measured at concentrations of 1 to 100 × CMC for a given compound, but they are not concentration-dependent. Therefore, wetting properties may be measured at higher or lower concentrations.

[0219] One method involves using an optical contact angle goniometer to measure the contact angle. This device uses a digital camera and software to analyze the contour shape of a stationary liquid droplet on a surface to determine the contact angle.

[0220] Possible applications of the surface-active compounds disclosed herein include formulations for use in shampoos, hair conditioners, detergents, spot-free rinse solutions, floor and carpet cleaners, graffiti removers, crop protection wetting agents, crop protection auxiliaries, and aerosol spray coatings.

[0221] Those skilled in the art will understand that even slight differences between compounds can lead to significantly different surfactant properties, and therefore different compounds may be used for different substrates and different applications. Those skilled in the art will also understand that surfactant properties are not always predictable based on chemical structure, as will be further demonstrated below. For example, surfactant 9 and the comparative surfactant differ only in the number of methylene groups at R3, but they demonstrate different surfactant properties. Surprisingly, surfactant 9 exhibits superior activity, as further described below, while the comparative surfactant exhibits inferior surfactant properties.

[0222] The following non-limiting embodiments are given to demonstrate the different properties of different surfactants. In Table 1 below, the abbreviations of the surfactants are associated with their corresponding chemical structures.

[0223] [Table 1-1]

[0224] [Table 1-2]

[0225] [Table 1-3]

[0226] These compounds are effective as surfactants in any of the formulations envisioned by this disclosure and may be useful as wetting or foaming agents, dispersants, emulsifiers, and detergents.

[0227] The amount of the compounds disclosed herein used in the formulation may be as low as about 0.001% by weight, about 0.05% by weight, about 0.1% by weight, about 0.5% by weight, about 1% by weight, about 2% by weight, or about 5% by weight; or as high as about 8% by weight, about 10% by weight, about 15% by weight, about 20% by weight, or about 25% by weight, about 30% by weight, about 40% by weight, about 50% by weight, or about 80% by weight; or within any range of 0.001% to 80% by weight, or 0.05% to 50% by weight, or 0.1% to 20% by weight, or 0.5% to 10% by weight, or 1% to 8% by weight, or 2% to 8% by weight, or 5% to 8% by weight, or any range using any two of the aforementioned values.

[0228] Table 2 includes comparative surfactants, including their names and structures.

[0229] [Table 2]

[0230] Useful surfactants in the formulations disclosed herein may have a critical micelle concentration (CMC) of less than about 15 mmol, less than about 10 mmol, less than about 5 mmol, less than about 1 mmol, less than about 0.8 mmol, less than about 0.7 mmol, less than about 0.6 mmol, less than about 0.5 mmol, less than about 0.4 mmol, less than about 0.3 mmol, less than about 0.2 mmol, less than about 0.1 mmol, less than about 0.05 mmol, or less than about 0.01 mmol, or may have any CMC within the range encompassed by the aforementioned endpoints. For example, a surfactant may have a CMC of about 0.01 to about 15 mmol, about 0.05 to about 10 mmol, or about 0.1 to about 5 mmol.

[0231] Useful surfactants in the formulations disclosed herein may have minimum surface tension plateau values ​​of less than about 25 mN / m, less than about 24 mN / m, less than about 23 mN / m, less than about 22 mN / m, less than about 21 mN / m, less than about 20 mN / m, less than about 19 mN / m, less than about 18 mN / m, less than about 17 mN / m, less than about 16 mN / m, or less than about 15 mN / m, or they may have any minimum surface tension plateau value within the range encompassed by the aforementioned endpoints. For example, a surfactant may have a minimum surface tension plateau value of about 15 to about 25 mN / m, about 18 to about 22 mN / m, or about 20 to about 21 mN / m. [Examples]

[0232] Nuclear magnetic resonance (NMR) spectroscopy was performed using a Bruker 500 MHz spectrometer. The critical micelle concentration (CMC) was determined at 23°C using a Wilhelmie plate method with a tensile strength meter (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate. Dynamic surface tension was determined at 23°C using a bubble pressure tensile strength meter (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.

[0233] Example 1: Synthesis of 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)hexanamide 6-(dimethylamino)hexanoic acid (2.00 g, 12.56 mmol, 1 equivalent) was dissolved in toluene (50 mL) in a 100 mL round-bottom boiling flask equipped with a Dean-Stark trap, and then 3-aminopropyltris(trimethylsiloxy)silane (5.48 mL, 13.81 mmol, 1.1 equivalents) was added. The reaction vessel was heated and the reaction mixture was refluxed for 24 hours until no more water separated into the Dean-Stark tube. The solvent was removed under vacuum to obtain the desired siloxane derivative as a yellow oil in 94% yield. 1 H NMR (500 MHz, DMSO) δ: 0.09 (s, 27H), 0.28-0.31 (m, 2H), 1.12-1.26 (m, 2H), 1.27-1.30 (m, 4H), 1.38-1.41 (m, 2H), 1.94 (t, J = 7.3 Hz, 2H), 2.00 (s, 6H), 2.06-2.03 (m, 2H), 2.89 (dd, J = 12.9, 6.8 Hz, 2H).

[0234] Example 2a: Synthesis of N-benzyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide (surfactant 1)

[0235] [ka]

[0236] The siloxane derivative described in Example 1 (1 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). Benzyl bromide (518 mg, 3.03 mmol) was added, and the mixture was heated at 70°C for 12 hours. The solvent was removed under vacuum, and the crude product was washed twice with acetone to remove excess benzyl bromide, yielding surfactant 1 as a yellow solid (1.1 g).

[0237] Example 2b: Determination of the physical properties of surfactant 1 The critical micelle concentration (CMC) of surfactant 1 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 9.883 mmol at pH 8. The minimum surface tension plateau value achievable with this surfactant was approximately 20.67 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted in Figure 1 as surface tension versus concentration.

[0238] Example 3a: Synthesis of N-(2-ethoxy-2-oxoethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide (surfactant 2)

[0239] [ka]

[0240] The siloxane derivative described in Example 1 (1 g, 2.02 mmol) was dissolved in DMF (15 mL), and ethyl bromoethyl (0.25 mL, 2.4 mmol) was added. The mixture was stirred at 70°C for 12 hours. The solvent was removed under vacuum, and the crude product was washed twice with hexane to obtain surfactant 2 as a brown liquid (900 mg).

[0241] Example 3b: Determination of the physical properties of surfactant 2 The critical micelle concentration (CMC) of surfactant 2 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.2171 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.36 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted in Figure 2 as surface tension versus concentration.

[0242] Example 4a: Synthesis of N-allyl-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium iodide (surfactant 3)

[0243] [ka]

[0244] To acetonitrile (10 mL), the siloxane derivative described in Example 1 (1.00 g, 2.02 mmol), followed by sodium carbonate (0.26 g), and then allyl iodide (674 mg) was added. The reaction mixture was refluxed at 40°C for 14 hours. Residual sodium carbonate was removed by filtration, and the filtrate was concentrated. To remove excess allyl iodide, the crude product was washed twice with hexane to obtain surfactant 3 as a brown liquid (850 mg).

[0245] Example 4b: Determination of the physical properties of surfactant 3 The critical micelle concentration (CMC) of surfactant 3 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 1.3599 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.67 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted as surface tension versus concentration in Figure 3.

[0246] Example 5a: Synthesis of 6-((3-(1,1,1,5,5,5-Hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxo-N-(propa-2-in-1-yl)hexano-1-aminium bromide (surfactant 4)

[0247] [ka]

[0248] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). Propargyl bromide (674 mg, 2.4 mmol) was added, and the mixture was stirred at 70°C for 12 hours. The solvent was removed under vacuum, and the crude product was washed twice with hexane to obtain surfactant 4 as a brown liquid (850 mg).

[0249] Example 5b: Determination of the physical properties of surfactant 4 The critical micelle concentration (CMC) of surfactant 4 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.2419 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.54 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted in Figure 4 as surface tension versus concentration.

[0250] Example 6a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N-(2-(2-methoxyethoxy)ethyl)-N,N-dimethyl-6-oxohexane-1-aminium bromide (surfactant 5)

[0251] [ka]

[0252] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). 1-bromo-2-(2-methoxyethoxy)ethane (2.4 mmol) was added, and the mixture was stirred at 70°C for 12 hours. The solvent was removed under vacuum, and the crude product was washed twice with hexane to obtain surfactant 5 as a brown liquid (800 mg).

[0253] Example 6b: Determination of the physical properties of surfactant 5 The critical micelle concentration (CMC) of surfactant 5 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.4622 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.40 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted in Figure 5 as surface tension versus concentration.

[0254] Example 7a: Synthesis of N-(3-(diethoxyphosphoryl)propyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide (surfactant 6)

[0255] [ka]

[0256] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (20 mL). Bromophosphonate (4.04 mmol) was added, and the mixture was stirred at 70°C for 12 hours. The solvent was removed under vacuum, and the crude product was washed twice with hexane to obtain surfactant 6 as a brown liquid (900 mg).

[0257] Example 7b: Determination of the physical properties of surfactant 6 The critical micelle concentration (CMC) of surfactant 6 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.3989 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.48 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted in Figure 6 as surface tension versus concentration.

[0258] Example 8a: Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N-(3-hydroxypropyl)-N,N-dimethyl-6-oxohexane-1-aminium iodide (surfactant 7)

[0259] [ka]

[0260] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in acetonitrile (10 mL). Sodium carbonate (0.26 g), followed by 3-iodopropanol (674 mg), was added. The mixture was stirred at 40°C for 24 hours. Residual base was removed by filtration, and the filtrate was concentrated. The crude product was washed twice with hexane to remove excess iodopropanol, and surfactant 7 was obtained as a brown liquid (780 mg).

[0261] Example 8b: Determination of the physical properties of surfactant 7 The critical micelle concentration (CMC) of surfactant 7 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.4568 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.61 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted in Figure 7 as surface tension versus concentration.

[0262] Example 9a: Synthesis of 6-((3-(1,1,1,5,5,5-Hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-6-oxohexane-1-aminium iodide (surfactant 8)

[0263] [ka]

[0264] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in acetonitrile (10 mL). 2-iodoethanol (4.04 mmol) was added, and the mixture was stirred at 40°C for 14 hours. The solvent was removed, and the crude product was washed twice with hexane to obtain surfactant 8 (910 mg).

[0265] Example 9b: Determination of the physical properties of surfactant 8 The critical micelle concentration (CMC) of surfactant 8 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.9986 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.41 mN / m, indicating that the surfactant possesses significant surface activity. These results are plotted in Figure 8 as surface tension versus concentration.

[0266] Example 10a: N 1 ,N 3 -Bis(6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)-N 1 ,N 1 ,N 3 ,N 3 Synthesis of tetramethylpropane-1,3-diaminium dibromide (surfactant 10)

[0267] [ka]

[0268] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (20 mL). 1,2-dibromopropane (1 mmol) was added, and the mixture was stirred at 70°C for 12 hours. The solvent was removed, and the crude product was washed twice with hexane to obtain surfactant 10 as a brown liquid (900 mg).

[0269] Example 10b: Determination of the physical properties of surfactant 10 The critical micelle concentration (CMC) of surfactant 10 was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.0631 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 22.12 mN / m, indicating that the surfactant possesses surface activity. These results are plotted in Figure 10 as surface tension versus concentration.

[0270] Example 11a: Synthesis of N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide (surfactant 9)

[0271] [ka]

[0272] The siloxane derivative described in Example 1 (1 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL), and 6-bromohexanoic acid (2.02 mmol) was added. The mixture was stirred at 70°C for 12 hours, and then the solvent was removed under vacuum. The crude product was washed twice with hexane to obtain N-(5-carboxypentyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide as a viscous brown liquid (650 mg).

[0273] Example 11b: Determination of the physical properties of surfactant 9 The critical micelle concentration (CMC) of surfactant 9a was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 0.2237 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 20.52 mN / m, demonstrating that this surfactant possesses excellent surface activity. These results are plotted in Figure 9 as surface tension versus concentration.

[0274] Comparative Example A1: Synthesis of N-(carboxymethyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide (comparative surfactant)

[0275] [ka]

[0276] The siloxane derivative described in Example 1 (1.00 g, 2.02 mmol) was dissolved in dimethylformamide (DMF) (15 mL). Bromoacetic acid (2.02 mmol) was added, and the mixture was stirred at 70°C for 12 hours. The solvent was removed, and the crude product was washed twice with hexane to obtain surfactant 9b as a brown liquid (700 mg).

[0277] Comparative Example A2: Determination of the physical properties of the comparative surfactant. The critical micelle concentration (CMC) of surfactant 9b was measured. From the change in surface tension with respect to concentration in water, the CMC was determined to be approximately 17.28 mmol. The minimum surface tension plateau value achievable with this surfactant was approximately 29.16 mN / m. These results are plotted in Figure 11 as surface tension versus concentration. The results illustrate the difficulty in predicting surfactant activity based on chemical structure; surfactant 9, which differs only in the number of methylene groups in the carboxylic acid, exhibits remarkably superior activity.

[0278] Example 12: Synthesis of N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide (surfactant 11)

[0279] [ka]

[0280] 4-(4-bromobutyl)benzoic acid is added to the siloxane derivative described in Example 1 to obtain N-(4-(4-carboxyphenyl)butyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide.

[0281] Example 13: Synthesis of N-(4-carboxybenzyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide (surfactant 12)

[0282] [ka]

[0283] 4-(bromomethyl)benzoic acid is added to the siloxane derivative described in Example 1 to obtain N-(4-carboxybenzyl)-6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium bromide.

[0284] Example 14 Fracking fluid One composition of the present invention comprises a mixture of water, a water-soluble block copolymer, a nonionic surfactant, and an inorganic salt containing monovalent and / or divalent and / or trivalent ions. A preferred composition of the present invention contains a mixture of water and a water-soluble block copolymer. The proportionate amounts of the above-named components in the composition may vary. Typically, the composition has, on a wet basis, 0.05 to 20% by weight of the water-soluble block copolymer, 0.01 to 10% by weight of the nonionic surfactant, and 0.1 to 20% by weight of the inorganic salt containing monovalent and / or divalent and / or trivalent ions. The water-soluble monovalent and / or divalent electrolyte is typically used in amounts of about 1% by weight to about 15% by weight, or about 1 to 10% by weight, based on the weight (wet basis) of the aqueous composition.

[0285] Some compositions of the present invention comprise water and a mixture of water-soluble block copolymers. Preferred compositions of the present invention comprise water, a water-soluble block copolymer polymer, an inorganic salt, and a mixture of nonionic surfactants, and essentially do not contain anionic surfactants.

[0286] The proportions of the components named above in the composition may vary. Typically, the composition has 0.05 to 20% by weight of a water-soluble block copolymer on a wet basis, 0.01 to 10% by weight of a nonionic surfactant, and 0.1 to 20% by weight of an inorganic salt containing monovalent and / or divalent and / or trivalent ions. The water-soluble monovalent and / or divalent electrolyte is typically used in amounts of about 1% by weight to about 15% by weight, or about 1 to 10% by weight, of the aqueous composition based on the weight of the aqueous composition (on a wet basis).

[0287] The proportions of the components named above in the composition may vary. However, for the water-soluble block copolymers and nonionic surfactants in the total compositions of some embodiments of the present invention, typical ranges are listed in Table 3 on a wet basis.

[0288] [Table 3]

[0289] Water-soluble inorganic salts contain monovalent and / or divalent and / or trivalent ions. Inorganic salt concentrations are typically used in amounts of about 0.01% to about 20% or about 1% to about 15% based on the weight of the aqueous medium, for example, in amounts of about 1 to 10%.

[0290] Example 15 Fracking Fluid Non-limiting examples of the formulations of the present invention include the compositions listed in Table 4.

[0291] [Table 4]

[0292] Example 16: Demulsification of corn oil The corn oil demulsification properties of formulations 1 through 16 were investigated in Table 8 below. Each formulation exhibited corn oil demulsification properties.

[0293] Non-limiting examples of the formulations of the present invention include the compositions listed in Table 5.

[0294] [Table 5]

[0295] Example 17: Improved oil recovery fluid An example composition of an injection fluid suitable for improving the recovery of oil or gas from wells is as follows: (a) 0.01 to 5% by weight of one or more surfactants of the present invention, (b) aqueous injection fluid, (c) 0-5% by weight of one or more alkalis, (d) 0-1% of one or more viscosity enhancers, (e) 0-50% by weight of one or more cosolvents, (f) 0-50% by weight of one or more cosurfactants, and (g) 0-5% by weight of one or more cosurfactants. The aqueous carrier includes, but is not limited to, water, produced brine, river water, synthetic brine, and seawater.

[0296] Example 18: Formulation for recovering corn oil from distillation wastewater Several exemplary corn oil extract formulations are summarized in Table 6 as corn oil demulsification formulations numbered 1-16. Each formulation possesses corn oil demulsification properties.

[0297] The polyglycerol ester was 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 containing C8-C10 alkyl groups and an average of 1.7 glucose units per mole of alkyl polyglucoside.

[0298] The PEG 400 used was polyethylene glycol with an average molecular weight of 400 daltons. The PEG 400 MO used was polyethylene glycol monooleate with an average molecular weight of 400 daltons. The PEG 400 DO used was polyethylene glycol dioleate with an average molecular weight of 400 daltons.

[0299] The PEG 400 mono soyate used is an ester of polyethylene glycol (with an average molecular weight of 400 daltons) and fatty acids derived from soybean oil. Soybean oil is typically a triglyceride containing the following fatty acids: myristic acid 0.1%, palmitic acid 11.0%, and palmitoleic acid %.

[0300] At least one of the surfactants of the present invention, such as that described in Formula 1, is added to each formulation.

[0301] [Table 6-1]

[0302] [Table 6-2]

[0303] manner Embodiment 1 is at least one surfactant of formula I:

[0304] [ka]

[0305] [In the formula, R 1 and R 2 The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group comprising at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. The fracking fluid formulation also optionally contains a polymer or a viscoelastic surfactant.

[0306] Embodiment 2 is at least one surfactant of formula I:

[0307] [ka]

[0308] [In the formula, R 1 and R 2 The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group comprising at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. The oil-enhancing oil recovery formulation also optionally comprises at least one additional surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, sulfonate surfactants, sulfate surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants, an aqueous phase, a polymer, an inorganic salt, a thickener, a water-immiscible solvent, and a water-miscible solvent.

[0309] Embodiment 3 is at least one surfactant of formula I:

[0310] [ka]

[0311] [In the formula, R 1 and R 2The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group comprising at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chlorides, bromides and iodides; and any gas including, but not limited to, any combination of any of the following gases; the gas may be air, nitrogen, carbon dioxide and natural gas; optionally, at least one additional surfactant, e.g., sulfonate surfactant, sulfate surfactant, cationic surfactant, nonionic surfactant, zwitterionic surfactant, sulfonate surfactant, sulfate surfactant, cationic surfactant, nonionic surfactant, zwitterionic surfactant; aqueous phase; polymer; inorganic salt; thickener; water-immiscible solvent and / or water-miscible solvent; a formulation for a foaming emulsion.

[0312] Embodiment 4 is at least one surfactant of formula I:

[0313] [ka]

[0314] [In the formula, R 1 and R 2The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyls, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chlorides, bromides, and iodides; and optionally, a bio-based oil recovery formulation comprising lecithin and / or at least one modified lecithin, comprising derivatives of lecithin formed by any of the following processes: acetylation, hydroxylation, hydrogenation, hydrolysis products, chlorination, bromination, iodation, halogenation, phosphorylation, and / or sulfonation of lecithin.

[0315] Embodiment 5 is a method for recovering hydrocarbons, the method comprising the step of injecting or otherwise introducing any of the formulations, any combination of the formulations, or any element of any of the formulations described in Embodiments 1 to 3 of this Disclosure into an oil and / or gas well, the formulations may be formed before or after the components of the formulations are introduced into the well; Further steps of the method include recovering oil and / or gas from the well after or during the addition of the formulation of the present invention to the well. Hydrocarbon recovery methods that may utilize the surfactants and / or formulations disclosed herein include, but are not limited to, fracking, enhanced oil and / or gas recovery, stripping, irritation, drilling, cementing, sealing and gas lifting.

[0316] Embodiment 6 includes a method for recovering bio-based oil from natural sources such as plants, including fruits, seeds, grains, and algae, from processes such as alcohol production, biodiesel production, and oil intended for human or animal consumption, the method comprising the step of bringing the bio-oil source into contact with any of the formulations of the present invention or with any element of the formulations of the invention described in Embodiments 1 to 4 of this disclosure, the formulation of Embodiment 4 may be preferred for these methods, and these processes may further include the step of separating the formulation and / or bio-oil from the source, and optionally separating at least some elements of the formulations of the invention from the bio-oil. If the final use of the recovered bio-oil is for use in human food or animal feed, the preferred formulation consists only of GRAS components.

[0317] Embodiment 7 is Equation I

[0318] [ka]

[0319] [In the formula, R 1 and R 2 The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyls, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. The compound of formula I is used as a surfactant in a fracking fluid formulation containing at least one surfactant.

[0320] Embodiment 8 is Equation I:

[0321] [ka]

[0322] [In the formula, R 1 and R 2 The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyls, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. The use of the compound of formula I as a surfactant in an enhanced oil recovery formulation comprising at least one surfactant, optionally at least one additional surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, sulfonate surfactants, sulfate surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants, an aqueous phase, a polymer, an inorganic salt, a thickener, a water-immiscible solvent, and a water-miscible solvent.

[0323] Embodiment 9 is Equation I:

[0324] [ka]

[0325] [In the formula, R 1 and R 2 The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyls, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. The compound of formula I is used as a surfactant in a foaming emulsion formulation containing at least one surfactant and a gas.

[0326] Embodiment 10 is Equation I:

[0327] [ka]

[0328] [In the formula, R 1 and R 2 The groups are the same or different and comprise at least one group selected from the group consisting of C1-C6 alkyl groups, optionally comprising one or more oxygen, nitrogen, or sulfur atoms, or a group comprising at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R 3 Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, alkyl phosphonate, C3-C8 carboxylic acid, C1-C 10 Alkylbenzoic acid, and C1-C bonded to the second molecule of formula I 12 Selected from the group consisting of linkers, the second molecule of formula I is either the same as or different from the first molecule of formula I; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. The use of the compound of formula I as a surfactant in a bio-based oil recovery formulation comprising at least one surfactant, optionally lecithin and / or at least one modified lecithin.

Claims

1. A hydrocarbon recovery compound, of formula I: 【Chemistry 1】 [In the formula, R １ and R ２ They are the same or different, C １ ~C ６ It comprises at least one group selected from the group consisting of alkyl groups, and optionally the C １ ~C ６ The alkyl group may contain one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R ３ is selected from the group consisting of alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, C ３ -C ８ carboxylic acid, C １ -C １０ alkylbenzoic acid, and C １ -C ６ linker attached to the second molecule of Formula I, and the second molecule is the same or different; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. At least one surfactant of the following: and aqueous phase A compound containing the following:

2. The formulation according to claim 1, further comprising at least one additional surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants, and anionic surfactants having a hydrophobic chain of 12 to 24 carbon atoms.

3. The formulation according to claim 1 or 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.

4. The formulation according to any one of claims 1 to 3, further comprising at least one polymer selected from the group consisting of quaternary ammonium compounds and anionic surfactants.

5. The formulation according to any one of claims 1 to 4, further comprising lecithin or modified lecithin.

6. The formulation according to any one of claims 1 to 5, further comprising at least one water-immiscible solvent.

7. The formulation according to any one of claims 1 to 6, further comprising at least one water-miscible solvent.

8. The composition according to any one of claims 1 to 7, further comprising at least one gas selected from the group consisting of air, nitrogen, carbon dioxide, and natural gas.

9. The formulation according to any one of claims 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 agents, disintegration retarders, particles, propane, gaseous components, disintegration aids, oxygen scavengers, alcohol, scale inhibitors, corrosion inhibitors, fluid loss additives, biocides / bactericides, friction reducers, and latex.

10. A method for recovering hydrocarbons, The steps include: preparing at least one formulation according to any one of claims 1 to 9; The step of injecting at least one of the aforementioned formulations into a well; A method comprising the steps of injecting the compound into the well and recovering the substance from the well.

11. A method for recovering hydrocarbons, The steps include: preparing at least one formulation according to any one of claims 1 to 9; The steps include: mixing the aforementioned compound with a substance containing bio-oil; A method comprising the step of recovering the bio-oil from the mixture.

12. The method according to claim 11, wherein the substance containing the bio-oil is distillation wastewater.

13. A method for recovering hydrocarbons, The process includes the steps of introducing a foaming fluid composition into an oil well or gas well, and performing an operation using the foaming fluid composition, The foaming composition is a base fluid containing an oil-based or water-based fluid; gas, Formula I: 【Chemistry 2】 [In the formula, R １ and R ２ They are the same or different, C １ ~C ６ It comprises at least one group selected from the group consisting of alkyl groups, and optionally the C １ ~C ６ The alkyl group may contain one or more oxygen, nitrogen, or sulfur atoms, or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; R ３ Alkenyl, alkynyl, ester, alcohol, arylalkyl, alkoxyalkyl ether, alkyl phosphate, C ３ ~C ８ Carboxylic acid, C １ ~C １０ Alkylbenzoic acid, and C bonded to the second molecule of formula I １ ~C ６ Selected from the group consisting of linkers, the second molecule may be the same or different; n is an integer between 1 and 12; X is selected from the group consisting of chloride, bromide, and iodide. A method comprising at least one surfactant.

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

15. Use of the formulation according to any one of claims 1 to 9 for the recovery of hydrocarbons.

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