Method for gas hydrate inhibition using a blend of an Anti-agglomerant with 2‑alkenyl and 2-alkyl imidazolines

Abstract

Disclosed herein is a method for inhibiting gas hydrate agglomerates / plugs by contacting hydrocarbon-water systems with a composition comprising: an amphiphile (A) of the formula R5-L-N(R1)(R2) or [R5-L-N(R1)(R2)(R3)]q+ [X-]q where: R1, R2 are each a C1-C8 alkyl or form heterocycle R3 is H or a C1-C8 alkyl (optional hydroxyl and / or carboxy) L is a linking moiety with ≥2 carbon atoms and N and / or O heteroatoms R5 is a C6 -C24 hydrocarbyl X- is an anion q is 0 or an integer from 1 to 7; and a surfactant (B) with an imidazoline head group and a C9-C19 linear hydrocarbyl tail. The A:B weight ratio ranges from 95:5 to 5:95.

Description

[0001] Clariant International Ltd 1

[0002] METHOD FOR GAS HYDRATE INHIBITION USING A BLEND OF AN ANTI- AGGLOMERANT WITH 2-ALKENYL AND 2-ALKYL IMIDAZOLINES

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims the benefit of priority of U.S. Provisional Patent Application no. 63 / 729,195, filed December 6, 2024, which is hereby incorporated herein by reference in its entirety.

[0005] TECHNICAL FIELD

[0006] The present disclosure relates to the prevention of gas hydrate blockage in oil and natural gas pipelines containing low-boiling point hydrocarbons and water. More specifically, the invention relates to a method of inhibiting gas hydrate blockage through the addition of gas hydrate inhibitor and a surfactant.

[0007] BACKGROUND

[0008] Gas hydrates are typically solids that may form in a fluid that is flowing or is substantially stationary, under certain temperature and pressure conditions. For example, gas hydrates may form during hydrocarbon production from a subterranean formation, in pipelines and other equipment during production operations. Hydrates may impede or completely block flow of hydrocarbons or other fluid flowing through such pipelines. These blockages not only may decrease or stop production, potentially costing millions of dollars in lost production, but also may be very difficult and dangerous to mediate. Unless properly handled, gas hydrates may be volatile and even explosive, potentially rupturing pipelines, damaging equipment, endangering workers, and causing environmental harm.

[0009] Gas hydrates may form when water molecules become bonded together after coming into contact with certain "guest" gas or liquid molecules. Hydrogen bonding may cause the water molecules to form a regular lattice structure, like a cage, that is stabilized by the guest gas or liquid molecules entrapped within the lattice structure. The resulting crystalline structure may precipitate as a solid gas hydrate. Guest molecules can include any number of molecules such as, for example, carbon dioxide, hydrogen, and low molecular weight hydrocarbons including methane, ethane, propane, n-butane, iso-butane, n-pentane, iso-pentane, and the like, and combinations of these gases as for example natural gas.

[0010] There are two basic chemical techniques to overcome or control the gas hydrate problems, namely thermodynamic hydrate inhibitors (TH Is) and low dose hydrate inhibitors (LDHIs). Thermodynamic hydrate inhibitors, such as methanol or one of the glycols, have traditionally been used to prevent hydrate formations. The thermodynamic inhibitors are effective at dosages of 5-50 wt.-% (or higher) based on the amount of water. As oil companies are exploring new production in deep waters, the total gas / oil / water production is increasing. The use of thermodynamic inhibitors is not viable in these applications due to logistical constraints of supplying and pumping such vast quantities of fluids to often remote locations.

[0011] Low dosage hydrate inhibitors (LDHIs) can overcome these logistical challenges. There are two main categories of LDHIs: Kinetic Hydrate Inhibitors and Anti- Agglomerants. Kinetic Hydrate Inhibitors (KHIs) are designed to prevent hydrate formation altogether, allowing fluids to be transported before catastrophic hydrate plugging occurs. They work by delaying or preventing the nucleation and growth of hydrate crystals. KHIs contain molecular moieties similar to the guest gas molecules that stabilize hydrate structures. It is proposed that KHIs disrupt crystal growth by incorporating into the growing hydrate lattice, distorting the cage structures required for further growth. For complete inhibition, the growing hydrates must assimilate the KHI moieties that resemble partial hydrate cages. While effective in both liquid hydrocarbon and aqueous phases, KHI performance tends to diminish at higher production pressures. Examples include polymers like poly(N-methylacrylamide), poly(N,N-dimethylacrylamide), poly(N-ethylacrylamide), poly(N,N- diethylacrylamide), poly(N-methyl-N-vinylacetamide), poly(2-ethyloxazoline), poly(N-vinylpyrrolidone), poly(N-vinylcaprolactam), and their copolymers.

[0012] The second major class of LDHIs are the anti-agglomerants (AAs). Unlike KHIs that delay or prevent hydrate nucleation and growth, acting as "anti-nucleators", AAs allow hydrate crystals to form but keep them dispersed as fine particles in the hydrocarbon phase, creating a flowing hydrate slurry. The key function of AAs is to inhibit the agglomeration of hydrate particles, preventing them from accumulating into larger masses that can cause pipeline plugs and restrictions. Essentially, AAs stop the initially formed small hydrate crystals from adhering to each other and the pipe walls, enabling their transport as a dispersed slurry.

[0013] In contrast to KHIs, anti-agglomerants (AAs) are only effective in the presence of a liquid hydrocarbon phase. The hydrocarbon phase serves as the continuous medium to transport the dispersed hydrate particles in the form of a low-viscosity slurry along the pipeline. By preventing the agglomeration of hydrate crystals nucleating in the discontinuous water droplets, AAs inhibit the formation of larger crystalline masses that could restrict flow. The hydrate particles remain finely dispersed within the hydrocarbon continuous phase, allowing the low-viscosity hydrate slurry to be pumped through the pipeline without blockages.

[0014] SUMMARY

[0015] One class of anti-agglomerant compounds for preventing hydrate crystal agglomeration are quaternary ammonium and phosphonium salts. These contain at least three alkyl groups with four or five carbon atoms, along with a longer alkyl or alkenyl chain in the range of 8 to 20 carbon atoms. Examples include tributylhexadecylphosphonium bromide and tributylhexadecylammonium bromide, where the long hydrophobic tail promotes partitioning into the hydrocarbon phase while the quaternary head group inhibits hydrate agglomeration.

[0016] Another class of anti-agglomerants are amphiphilic carboxylic acid derivatives. These molecules possess a lipophilic alkyl chain coupled with a hydrophilic tertiary amino or ammonium head group. The amphiphilic nature allows them to reside at the hydrocarbon-water interface and efficiently prevent agglomeration of hydrate crystals nucleating in the aqueous phase by providing steric stabilization.

[0017] Despite these existing anti-agglomerant chemistries, there remains a need for improved hydrate inhibitors that can more effectively prevent agglomeration during oil and gas transportation and processing operations. Desirable attributes include lower dosage requirements for reduced chemical demand and environmental impact, as well as enhanced performance under the challenging high pressures, low temperatures, and high water cuts which may be encountered in deep-water production scenarios.

[0018] Further, to maintain pipeline integrity, ensure oil product quality, protect the environment, and comply with regulations, the oil industry requires alternatives to organic halide-based anti-agglomerates for use in export pipelines. Organic halides are banned in oil export pipelines for several critical reasons. These compounds can cause corrosion and damage to pipeline materials and refinery equipment, negatively impact product quality, lead to environmental contamination, pose safety hazards, and result in regulatory non-compliance and economic losses. In sum, there is a need to find anti-agglomerates that do not contain organic halides.

[0019] The present disclosure is directed to methods, compositions, and formulations for controlling gas hydrate agglomerates and / or plugs using an amphiphile in combination with a surfactant.

[0020] According to at least one embodiment, the present disclosure provides a method comprising bringing a system containing hydrocarbons and water into contact with at least one amphiphile (A) each of the formula (1a) or (1 b)

[0021] R5-L-N(R1)(R2) (1 a)

[0022] [R5— L— N(R1)(R2)(R3)]q+[X-]q(1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or R1and R2, together with the nitrogen to which they are attached, form a heterocycle;

[0023] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;

[0024] L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from the group consisting of nitrogen and oxygen, and optionally one or more further heteroatoms;

[0025] R5is a hydrocarbyl group having from 6 to 24 carbon atoms; X’ is an anion; and q is 0 or an integer from 1 to 7; and at least one surfactant (B), each comprising an imidazoline head group and a C9-C19 linear hydrocarbyl tail, wherein the at least one amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) of from 95:5 to 5:95.

[0026] According to at least one further embodiment, the present disclosure provides a hydrate inhibitor composition comprising at least one amphiphile (A) each of the formula (1a) or (1 b) R5-L-N(R1)(R2) (1 a)

[0027] [R5— L— N(R1)(R2)(R3)]q+[X-]q(1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or R1and R2, together with the nitrogen to which they are attached, form a heterocycle;

[0028] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;

[0029] L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from the group consisting of nitrogen and oxygen, and optionally one or more further heteroatoms;

[0030] R5is a hydrocarbyl group having from 6 to 24 carbon atoms;

[0031] X’ is an anion; and q is 0 or an integer from 1 to 7; and at least one surfactant (B), each comprising an imidazoline head group and a C9-C19 linear hydrocarbyl tail, wherein the at least one amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) of from 95:5 to 5:95.

[0032] According to at least one further embodiment, the present disclosure provides a formulation comprising at least one amphiphile (A) of the formula (1 a) or (1 b) R5-L-N(R1)(R2) (1 a)

[0033] [R5— L— N(R1)(R2)(R3)]q+[X-]q(1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or the nitrogen atom, R1, and R2groups together form a heterocycle;

[0034] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;

[0035] L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from the group consisting of nitrogen and oxygen, and optionally one or more further heteroatoms;

[0036] R5is a hydrocarbyl group having from 6 to 24 carbon atoms;

[0037] X’ is an anion; and q is 0 or an integer from 1 to 7; and at least one surfactant (B), each comprising an imidazoline head group and a C9-C19 linear hydrocarbyl tail, wherein the at least one amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) of from 95:5 to 5:95.

[0038] Additional features and advantages will be set forth in the detailed description that follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows and the claims. It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.

[0039] DETAILED DESCRIPTION The present disclosure relates to a method of inhibiting the formation of gas hydrate utilizing a synergistic combination of an amphiphile (A) and at least one surfactant (B).

[0040] Herein, the “amphiphile (A)” may, interchangeably, be referred to as “the amphiphile,” “component (A),” or just “(A).” Herein, the “at least one surfactant (B)” may, interchangeably, be referred to as “the at least one surfactant,” “component (B),” or just “(B).”

[0041] The terms "hydrate" and "gas hydrate" are used interchangeably and refer to a gaseous mixture in a water clathrate — a solid hydrogen-bonded network of water molecules encapsulating gas molecules to form a cage-like structure. These terms particularly refer to hydrates formed by low molecular weight hydrocarbons, especially methane, ethane, and mixtures thereof, such as in natural gas. Correspondingly, "hydrate inhibitor" and "gas hydrate inhibitor" refer to additives that inhibit, retard, mitigate, reduce, control, or delay the formation of hydrates, their agglomerates, or plugs.

[0042] "Formation" or "forming" of hydrates encompasses any creation of hydrate solids from water and gases (especially hydrocarbons), their growth, agglomeration, accumulation on surfaces, and any related system problems. "Gas hydrate inhibitor performance" refers to the ability to prevent or mitigate the agglomeration of gas hydrates or gas hydrate-forming compounds. "Inhibiting" or "inhibited" means any improvement in preventing, reducing, retarding, mitigating, controlling, or delaying hydrate formation, growth, or agglomeration, particularly for light hydrocarbon gas hydrates.

[0043] In the context of this disclosure, "synergy" refers to the enhanced performance achieved by combining components (A) and (B) compared to their individual use at the same total dose rate. This synergy can manifest in two ways:

[0044] 1 . at a given dose rate, the performance of (A)+(B) exceeds the sum of their individual performances; and / or 2. to achieve a specific performance level, a lower total dose of (A)+(B) is required compared to using either component alone.

[0045] The key metric is the reduced total dose rate needed to prevent hydrate agglomeration when (A) and (B) are combined versus their separate use. This reduction is particularly beneficial in high water cut scenarios where production might otherwise become unfeasible. By significantly reducing the required dosage of inhibitors, this innovative method addresses multiple challenges simultaneously. It extends the operational life of aging production facilities by making previously uneconomical high water cut fields viable, reduces logistical burdens associated with chemical handling, mitigates environmental impacts, and offers substantial cost savings. Furthermore, it increases operational flexibility by expanding the range of treatable water cuts. Ultimately, this advancement in gas hydrate inhibition technology has the potential to transform the economics and operational strategies of mature fields, contributing to more sustainable and efficient hydrocarbon production practices while bridging the gap between current energy needs and future solutions.

[0046] The present disclosure provides a method comprising bringing a system containing hydrocarbons and water into contact with at least one amphiphile (A) each of the formula (1a) or (1 b) R5-L-N(R1)(R2) (1 a)

[0047] [R5— L— N(R1)(R2)(R3)]q+[X’]q (1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or R1and R2, together with the nitrogen to which they are attached, form a heterocycle;

[0048] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;

[0049] L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from the group consisting of nitrogen and oxygen, and optionally one or more further heteroatoms; R5is a hydrocarbyl group having from 6 to 24 carbon atoms;

[0050] X’ is an anion; and q is 0 or an integer from 1 to 7; and at least one surfactant (B), each comprising an imidazoline head group and a C9-C19 linear hydrocarbyl tail, wherein the at least one amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) of from 95:5 to 5:95.

[0051] AMPHIPHILE (A)

[0052] The methods, compositions, and formulations disclosed herein use a gas hydrate inhibitor comprising at least one amphiphile (A) each of the formula (1 a) or 1 (b),

[0053] R5-L-N(R1)(R2) (1 a)

[0054] [R5-L-N(R1)(R2)(R3)]q+[X’]q (1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or the nitrogen atom, R1, and R2groups together form a heterocycle;

[0055] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;

[0056] L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from the group consisting of nitrogen and oxygen, and optionally one or more further heteroatoms;

[0057] R5is a hydrocarbyl group having from 6 to 24 carbon atoms;

[0058] X’ is an anion; and q is 0 or an integer from 1 to 7.

[0059] Each amphiphile (A) comprises a head group -N(R1)(R2) or -N(R1)(R2)(R3) connected to a tail R5via a linking moiety L.

[0060] In some embodiments disclosed herein, the at least one amphiphile (A) comprises or consists of an amphiphile of formula (1 a) R5-L-N(R1)(R2) (1 a)

[0061] In some embodiments disclosed herein, the at least one amphiphile (A) comprises or consists of an amphiphile of formula (1 b)

[0062] [R5-L-N(R1)(R2)(R3)]q+[X-]q(1 b)

[0063] In some such embodiments, in one or more amphiphiles (e.g., each amphiphile) of the formula (1 b) the nitrogen carries a cationic charge, the linking moiety L does not carry any cationic charge, and q is 1 . In other such embodiments, in one or more amphiphiles (e.g., each amphiphile) of the formula (1 b) the nitrogen carries a cationic charge, the linking moiety L carries one or more cationic charges, and q is an integer between 2 and 7.

[0064] In various embodiments disclosed herein, each of R1and R2is, independently, an alkyl residue having 3, 4, or 5 carbon atoms. In some embodiments, R1and R2each contain 4 carbon atoms. In some embodiments, R1and R2are linear or, when containing at least three carbon atoms, are branched. In some embodiments, R1and R2are independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso-pentyl. In some embodiments, R1and R2are independently selected from the group consisting of n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso-pentyl. In some embodiments, R1and R2are independently selected from the group consisting of n- butyl, iso-butyl, and tert-butyl. The alkyl residues R1and R2may be the same or they may be different. In at least one embodiment, R1and R2are the same.

[0065] In some embodiments, R1and R2, together with the nitrogen to which they are attached, form a heterocycle. The heterocycle can be considered a "nitrogencontaining heterocycle". The nitrogen-containing heterocycle can be an optionally substituted, fully saturated or unsaturated, aromatic or nonaromatic group having at least one nitrogen atom in the ring. In some embodiments, the nitrogen-containing heterocycle is a monocyclic structure comprising a ring made up of 5 or 6 atoms. In some embodiments, the nitrogen-containing heterocycle is a bicyclic structure comprising two rings fused or otherwise connected. In some such embodiments, each ring of the bicyclic structure is made up of 5 or 6 atoms. In some embodiments, each ring of the monocyclic or bicyclic nitrogen-containing heterocycle can also contain 1 or 2 oxygen atoms or 1 or 2 sulfur atoms. Exemplary nitrogen-containing heterocycles include pyrrole, pyrroline, pyrrolidine, piperidine, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, triazole, isoxazole, isoxazoline, isoxazolidine, oxazole, oxazoline, oxazolidine, thiazole, isothiazole, oxadiazole, oxatriazole, dioxazole, oxathiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, oxazine, oxathiazine, oxazine, isoxazine, oxadiazine, morpholine, azepane, azepine, caprolactam, and quinoline. When substituted, the exemplary substituents can include one or more of the following groups: C1-C20 alkyl, C2-C20 alkenyl, aryl, aralkyl, hydroxyl, acyl, acyloxy, alkoxy, alkenoxy, aryloxy, halogen, amino, nitro, cyano, esters, and ethers.

[0066] In some embodiments ( / .e., in which the at least one amphiphile (A) includes an amphiphile of the formula 1 (b)), R3is hydrogen. This can be accomplished by the reaction of the above described tertiary amino group -N(R1)(R2) of formula (1 a) with an acid. The acid may be organic or inorganic. Preferred inorganic acids are halide acids like HCI, HBr and HI; sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, or a combination thereof. Preferred organic acids are carboxylic acids, sulfonic acids and phosphonic acids, as for example formic acid, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, glycolic acid, pivalic acid, malic acid, maleic acid, succinic acid, thioglycolic acid, methane sulfonic acid, p-toluene sulfonic acid, the like, and any combination thereof.

[0067] In some embodiments ( / .e., in which the at least one amphiphile (A) includes an amphiphile of the formula 1 (b)), R3is an alkyl group having from 1 to 8, from 1 to 5, or from 1 to 4 carbon atoms. In at least one such embodiment, R3is a methyl or an ethyl group. This can be accomplished by reaction of the above-described tertiary amino group -N(R1)(R2) of formula (1a) with an alkylating agent. The alkylating agent may include alkyl halides, alkyl sulfates, oxalates, carbonates, hydrocarbyl epoxides, and mixtures thereof. In some embodiments, the alkylating agent may be a sulfate, such as dimethyl sulfate. In some embodiments, the alkylating agent may be a halide, such as CH3CI. In some embodiments, the alkylating agent may be a carbonate, such as dimethyl carbonate. In some embodiments, the alkylating agent may be an epoxide, such as a hydrocarbyl epoxide, such as, for example, ethylene oxide, propylene oxide, butylene oxide, and the like. In some embodiments, the alkylating agent may be acrylic acid or methacrylic acid. In at least one embodiment, the alkylating agent is selected from the group consisting of methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, dimethyl sulfate, diethyl sulfate, and any combination thereof. In some embodiments wherein the alkyl group has at least 2 carbon atoms, the alkyl group is substituted with a hydroxyl group or a carboxyl group at the 2-position.

[0068] In the amphiphiles of formulas (1a) and (1 b), the head group is connected to a linking moiety L. In some embodiments, the linking moiety L comprises a total of from 5 to 200, from 5 to 100, from 5 to 50, from 5 to 20, from 5 to 10, from 10 to 200, from 10 to 100, from 10 to 50, from 10 to 20, from 20 to 200, from 20 to 100, or from 20 to 50 total atoms, excluding hydrogen atoms. For the purposes of counting atoms in the linking moiety L, starting from the lipophilic tail R5, the linking moiety begins at the first position where there is either a heteroatom or a carbon atom that is substituted with a group comprising at least one heteroatom.

[0069] The linking moiety L comprises a “connecting chain” that is made up of “linking elements.” In some embodiments, the linking elements forming the connecting chain can be carbon atoms or heteroatoms. In some embodiments, the connecting chain contains from 3 to 160, from 20 to 140, from 40 to 120, or from 60 to 100 linking elements. In some embodiments, the connecting chain contains from 4 to 20, from 5 to 20, from 6 to 20, from 4 to 14, from 5 to 14, from 6 to 14, from 4 to 12, from 5 to 12, from 6 to 12, from 4 to 10, from 5 to 10, or from 6 to 10 linking elements.

[0070] The connecting chain can comprise one or more aliphatic groups having from 2 to 10, from 3 to 6, or from 2 to 4 adjacent carbon atoms. In such embodiments, the aliphatic groups are selected from the group consisting of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. In at least one embodiment, the connecting chain comprises from 2 to 4 adjacent carbon atoms.

[0071] In some embodiments, the connecting chain comprises a saturated or unsaturated “heteroaliphatic chain,” herein defined as a linear or branched chain of carbon atoms that is interrupted by at least one heteroatom. In some embodiments, at least some of the carbon atoms in the connecting chain are connected to each other and / or to the hydrophobic tail by a heteroatom. In some embodiments, one or more hydrocarbyl segments each having from 2 to 10, from 3 to 6, or from 2 to 4 adjacent carbon atoms are connected to each other and / or to the hydrophobic tail by a heteroatom. In some such embodiments, the heteroatom is a nitrogen or oxygen atom. In some embodiments, not more than one heteroatom is connected to an individual carbon atom.

[0072] In some embodiments, the connecting chain is a heteroaliphatic chain made up of at least 2 adjacent carbon atoms and at least one heteroatom selected from the group consisting of oxygen and nitrogen. In some such embodiments, the connecting chain can include one or more additional heteroatoms. In some embodiments, the one or more additional heteroatoms are selected from the group consisting of nitrogen, oxygen, phosphorous, and sulfur. In some such embodiments, at least one of the one or more additional heteroatoms is a nitrogen or an oxygen atom.

[0073] In some embodiments, the atoms in the connecting chain are part of a functional group. In some embodiments, at least one atom in the connecting chain is part of a functional group selected from the group consisting of -C(=O)-O-, -0- C(=O)-, -C(=O)-N(R6)-, -C(=O)N(R6)-

[0074] -N(R7)C(=O)-, -N(R7)-C(=O), -N(R6)-, -(R7)N-, -O-, -S-, -(SO)- or -(SO2)-, wherein R6is hydrogen or an alkyl group having from 1 to 5 carbon atoms or from 3 to 5 carbon atoms and R7is hydrogen or an organic moiety having from 1 to 20 carbon atoms. In at least one embodiment, R6is hydrogen. In at least one embodiment, R6is an alkyl group having 4 carbon atoms. In at least one embodiment, R7is an alkyl group having from 1 to 20 carbon atoms.

[0075] In some embodiments, the connecting chain includes at least one carbon atom that is part of a carbonyl or a carboxymethyl group. In some embodiments, the connecting chain includes at least one nitrogen atom that is part of an amino, a polyamino, an ammonium, a polyammonium, an amide, or an imide group. In at least one embodiment, the connecting chain contains at least one nitrogen atom in the form of an amine or amide group. In some embodiments, the connecting chain contains one or more heteroatoms that are part of an ether, a polyether, an amino, a polyamino, an ammonium, or a polyammonium group. In some embodiments, the connecting chain contains one or more heteroatoms that are part of a functional group selected from the group consisting of an ester, an amide, and an imide group. In such embodiments, the carbon atom of the carbonyl group and the nitrogen or oxygen of the functional group are included as linking elements in the connecting chain. In at least one such embodiment, the connecting chain contains one or more heteroatoms that are part of an amide.

[0076] The connecting chain can be substituted or unsubstituted. In some embodiments, the connecting chain does not contain any substituents. In some embodiments, one or more atoms in the connecting chain are substituted with one or more heteroatoms. In some embodiments, these heteroatoms are part of a hydroxyl group, an amino group, a carboxylic acid group, or a carboxylate group. In some embodiments, the linking elements of the connecting chain can be substituted with to an alkyl group. In some embodiments, this alkyl group contains from 1 to 6 carbon atoms.

[0077] In some embodiments disclosed herein, the linking moiety L is selected from the group consisting of the chemical structures (2) to (12):

[0078] -C(=O)-N(R6)-(CH2)t- (2)

[0079] -N(R7)-C(=O)-(CH2)t- (3)

[0080] -N(R7)-(CH2)2-C(=O)-NH-(CH2)t- (4)

[0081] -N(R7)-C(=O)-(CH2)2-N(R6)-(CH2)t- (5)

[0082] -CH(OH)-CH2-N(R6)-(CH2)t- (6)

[0083] -CH(COOH)-CH2-C(=O)-N(R6)-(CH2)t- (7a)

[0084] -CH(CH2-COOH)-C(=O)-N(R6)-(CH2)t- (7b)

[0085] -CH(COOH)-CH2-C(=O)-[O-(CH2)t]v- (8a)

[0086] -CH(CH2-COOH)-C(=O)-[O-(CH2)t]v- (8b)

[0087] -N(R7)-C(=O)-(CH2)2-C(=O)-N(R6)-(CH2)t- (9)

[0088] -N(R7)-C(=O)-CH2-CH(OH)-C(=O)-N(R6)-(CH2)t- (10a)

[0089] -N(R7)-C(=O)-CH(OH)-CH2-C(=O)-N(R6)-(CH2)t- (10b)

[0090] -N(R7)-C(=O)-CH(OH)-CH(OH)-C(=O)-N(R6)-(CH2)t- (11 )

[0091] -N(R7)-C(=O)-C(OH)(CH2COOH)-CH2-C(=O)-N(R6)-(CH2)t- (12a)

[0092] -N(R7)-C(=O)-CH2-C(OH)(CH2COOH)-C(=O)-N(R6)-(CH2)t- (12b)

[0093] In some embodiments, t is 2, 3 or 4. In some embodiments, v is an integer from 1 to 30 or from 1 to 10. In some embodiments, R6is hydrogen or an alkyl group having from 1 to 5 or from 2 to 4 carbon atoms. In at least one embodiment, R6is an alkyl group having 4 carbon atoms. In some embodiments, R7is hydrogen or an organic moiety having from 1 to 20 carbon atoms. In at least one embodiment, R7is an alkyl group having from 1 to 20 carbon atoms. In some embodiments, the amino groups are in the form of an ammonium compound.

[0094] The linking moiety L is also connected to a lipophilic tail R5. In some embodiments, the lipophilic tail R5is a hydrocarbyl group having from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms. In various such embodiments, R5has a distribution such that at least 80 wt% of the R5groups are linear alkyl or alkenyl 8-14 carbons in length. In various such embodiments, R5has a distribution such that at least 60 wt% of the R5groups are linear alkyl or alkenyl 10-14 (e.g. , 11-13) carbons in length. In some embodiments, lipophilic tail R5is a linear, branched, or cyclic alkyl or alkenyl group. In various embodiments, R5is a linear alkyl or alkenyl group. In some embodiments, the lipophilic tail R5is selected from the group consisting of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, docosyl, tricosyl, tetracosyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, octadecadienyl, and eicosenyl. In at least one embodiment, the lipophilic tail R5is a mixture of hexadecenyl, octadecenyl, and eicosenyl. The alkyl- and alkenyl groups R5may be of natural or synthetic origin.

[0095] In some embodiments, X’ is at least one anion selected from the group consisting of hydroxide, carboxylate, halide, sulfate, nitrite, nitrate, organic sulfonate, organic sulfate, phosphate, and organic phosphonate. Suitable halide anions include, without limitation, fluoride, chloride, bromide, and iodide. Suitable carboxylates include, without limitation, anions stemming from carboxylic acids having from 1 to 20, from 2 to 20, from 3 to 20, from 1 to 12, from 2 to 12, from 3 to 12, from 1 to 6, from 2 to 6, or from 3 to 6 carbon atoms. In some embodiments, the carboxylic acid is aliphatic. The aliphatic carboxylic acids may be linear or branched and may be saturated or unsaturated. In some embodiments, the anion X’ is selected from the group consisting of formate, acetate, propionate, butyrate, pentanoate, hexanoate, acrylate, methacrylate, glycolate, malonate, succinate, trifluoroacetate, and mixtures thereof. In some embodiments, the anion X’ is selected from the group consisting of acetate, halide, acrylate, and methacrylate. In some embodiments, the anion X’ is acrylate. In some embodiments, the anion X’ is methylsulfate or ethylsulfate. In some embodiments, X’ is the anion of the acid used for protonation of the amino group. In some embodiments, X’ is the anion formed during reaction of the alkylating agent with the amino group.

[0096] In some embodiments, q is an integer from 1 to 7. In some embodiments, q is an integer from 2 to 7. In some embodiments, q is 1 or 2. In some embodiments, q is 1.

[0097] In some embodiments disclosed herein, the amphiphile (A) is of the general formula (13),

[0098] In at least one such embodiment, R1, R2, R3, R5, and X’ are as defined hereinabove and

[0099] R4is selected from the group consisting of -(CH2)t-, -[(CH2-CHR10)s]-, - (CH2-CHR10O)u-(CH2)t-, wherein s is 1 , 2, or 3, t is 2, 3, or 4, and u is an integer from 1 to 100;

[0100] R6is hydrogen or an alkyl group having from 1 to 5 or from 1 to 4 carbon atoms;

[0101] R7is hydrogen or an organic moiety having from 1 to 20 carbon atoms;

[0102] R8is hydrogen or an alkyl group having from 1 to 5 carbon atoms;

[0103] R9is hydrogen or an alkyl group having from 1 to 5 or from 1 to 4 carbon atoms;

[0104] R10is an alkyl group having from 1 to 4 carbon atoms; m is 0 or 2, n is 0 or 1 , o is 0 or 2, p is 0 or an integer from 1 to 5; and q is an integer from 1 to 7, provided that q is not more than the sum of n + p +1.

[0105] In some embodiments wherein the amphiphile (A) is of the general formula (13) and R4is -(CH2-CHR10O)u-(CH2)t-, R10is an alkyl group having from 1 to 4 carbon atoms. In some embodiments, u is an integer from 1 to 25, from 1 to 10, or from 1 to 5. In some embodiments, R6is a methyl or a butyl group. In some embodiments, R9is a methyl or a butyl group. In some embodiments, R7is as an alkyl group having from 1 to 20 carbon atoms. In some embodiments, R8is a methyl or a butyl group. In some embodiments wherein the amphiphile (A) is of the general formula (13), m is 0. In some embodiments, m is 2. In some embodiments, o is 0. In some embodiments, o is 2. In some embodiments, the sum of m + o is 2.

[0106] In some embodiments wherein the amphiphile (A) is of the general formula (13), n is 0. In some embodiments, n is 1. In some embodiments, p is 0. In some embodiments, p is an integer from 1 to 5. In some embodiments, n+p is an integer from 1 to 6. In some embodiments, n+p is 1.

[0107] In some embodiments wherein the amphiphile (A) is of the general formula (13), the number of anions q depends on the presence of R3, R8, and / or R9. In general, q is equal to the total number of R3, R8, and R9groups present. In some embodiments, q is an integer from 1 to 7 or from 2 to 6, depending on the value of n + p, provided that q is not more than n + p + 1 .

[0108] In some embodiments wherein the amphiphile (A) is of the general formula (13), m, n and o are all 0. In such embodiments, the amphiphile (A) is of the general formula (14),

[0109] In at least one such embodiment, R1, R2, R3, R5, and X’ are as defined hereinabove and

[0110] R4is selected from the group consisting of -(CH2)t- and -[(CH2-CHR10)s]-;

[0111] R6is hydrogen or an alkyl group having from 1 to 5 carbon atoms;

[0112] R10is an alkyl group having from 1 to 4 carbon atoms; p is an integer from 1 to 5; s is 1 , 2, or 3; t is 2, ,3 or 4; q is O or l . In at least one embodiment wherein the amphiphile (A) is of the general formula (14), p is 1 or 2, and in at least one embodiment, p is 1 . In at least one embodiment, R4is -(CH2)t- and t is 3. In at least one embodiment, R6is hydrogen. In at least one embodiment, R3is hydrogen and X’ is selected from the group consisting of hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate. In at least one embodiment, X’ is acrylate.

[0113] In various embodiments disclosed herein, the amphiphile (A) is of the general formula (14) and

[0114] R1and R2are each independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso-pentyl;

[0115] R3is present as hydrogen or as an alkyl group having from 1 to 5 carbon atoms;

[0116] R4is -(CH2)t-;

[0117] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0118] R6is present as hydrogen; p is 1 or 2; t is 2, 3, or 4; q is 1 ; and

[0119] X’ is selected from the group consisting of hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from the group consisting of acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0120] In various embodiments disclosed herein, the amphiphile (A) is of the general formula (14) and R1and R2are each independently selected from the group consisting of n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso-pentyl;

[0121] R3is present as hydrogen;

[0122] R4is -(CH2)t-;

[0123] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0124] R6is present as hydrogen;

[0125] P is 1 ; t is 3; q is 1 ; and

[0126] X’ is selected from the group consisting of hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from the group consisting of acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0127] In various embodiments disclosed herein, the amphiphile (A) is of the general formula (14) and

[0128] R1and R2are each n-butyl;

[0129] R3is present as hydrogen;

[0130] R4is -(CH2)t-;

[0131] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0132] R6is present as hydrogen;

[0133] P is 1 ; t is 3; q is 1 ; and X’ is selected from the group consisting of hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from the group consisting of acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0134] In various embodiments disclosed herein, the amphiphile (A) is of the general formula (14) and

[0135] R1and R2are each independently selected from the group consisting of n- butyl, iso-butyl, tert-butyl, n-pentyl, and iso-pentyl;

[0136] R3is present as an alkyl group having from 1 to 5 carbon atoms;

[0137] R4is -(CH2)t-;

[0138] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0139] R6is present as hydrogen;

[0140] P is 1 ; t is 3; q is 1 ; and

[0141] X’ is selected from the group consisting of hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from the group consisting of acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0142] In some embodiments wherein the amphiphile (A) is of the general formula (14), the amphiphile (A) according to formula (14) is the reaction product of (i) an N,N- dialkylaminoalkylamine of formula HN(R6)-R4-N(R1)(R2) with (ii) a fatty acid of formula R5-COOH, an ester of a fatty acid of formula R5-COOH with an alcohol having from 1 to 4 carbon atoms, or a fatty acid triglyceride. In some embodiments, the dialkylamino group of the N,N-dialkylaminoalkylamine either includes two alkyl groups independently selected from the group consisting of methyl, ethyl, propyl, and butyl, or R1and R2, together with the nitrogen atom to which they are attached, form a 5- or 6-membered heterocycle. In some embodiments, the N,N-dialkylaminoalkylamine is selected from the group consisting of N,N-dimethylaminoethylamine, N,N-dimethylaminopropylamine,

[0143] N,N-diethylaminoethylamine, N,N-diethylaminopropylamine,

[0144] N,N-dipropylaminoethylamine, N,N-dipropylaminopropylamine,

[0145] N,N-dibutylaminoethylamine, N,N-dibutylaminopropylamine,

[0146] N,N-dimethylaminopropylenediamine, N,N-dipropylaminopropylenediamine, N,N-dibutylaminopropylenediamine, N-(3-aminopropyl)pyrrolidine,

[0147] N-(3-aminopropyl)piperidine, and N-(3-aminopropyl)azepane. In some embodiments, the fatty acid, fatty acid ester, or the fatty acid triglyceride is derived from a plant source, such as vegetable oils, or from an animal source, such as tallow oil, or combinations thereof. In some embodiments, the amphiphile (A) according to formula (14) is the reaction product of an amine selected from the group consisting of 3-(dialkylamino)propylamine and 2-(dialkylamino)ethylamine with vegetable oil or tallow oil.

[0148] In some embodiments, the reaction product of (i) an N,N-dialkylaminoalkylamine with (ii) a fatty acid, a fatty acid ester, or a fatty acid triglyceride is neutralized with an acid or by quaternized with an alkylating agent. In some embodiments, the acid is selected from the group consisting of mineral acids and organic acids having from 1 to 20 carbon atoms. In some embodiments, the acid is selected from the group consisting of formic acid, acetic acid, chloroacetic acid, propionic acid, acrylic acid, and methacrylic acid. In some embodiments, the alkylating agent is selected from the group consisting of an organic halide, dimethyl sulfate, and C2-C4 alkylene oxides. In some embodiments wherein the alkylating agent is an organic halide, the alkylating agent is an alkyl halide having from 1 to 8 carbon atoms.

[0149] In at least one embodiment disclosed herein, the amphiphile (A) is of the formula (15), (16), or (17),

[0150] In some embodiments, R1, R2, R3, R5, and X’ are defined as hereinabove and

[0151] R4is -(CH2)t-, wherein t is 2, 3 or 4;

[0152] R6is hydrogen or an alkyl group having from 1 to 5 carbon atoms;

[0153] R7is hydrogen or an organic moiety having from 1 to 20 carbon atoms; each of R8and R9is hydrogen or an alkyl group having from 1 to 5 carbon atoms; and q is 0, 1 , or 2.

[0154] In some embodiments wherein the amphiphile (A) is of the formula (15), (16), or (17), t is 3.

[0155] In some embodiments wherein the amphiphile (A) is of the formula (15), (16), or (17), In some embodiments, R6is an alkyl group having from 2 to 4 carbon atoms. In some embodiments, R6is a methyl or a butyl group. In some embodiments, R7is an alkyl group having from 1 to 20 carbon atoms.

[0156] In some embodiments wherein the amphiphile (A) is of the formula (15), (16), or (17), R9is an alkyl group having from 2 to 4 carbon atoms. In some embodiments, R9is a methyl or a butyl group.

[0157] In some embodiments wherein the amphiphile (A) is of the formula (15), (16), or (17), R8is present as an alkyl group having from 2 to 4 carbon atoms. In some embodiments, R8is present as a methyl or a butyl group. In some embodiments wherein the amphiphile (A) is of the formula (15), (16), or (17), q is 0. In such embodiments, R3, R8, and R9are absent. In some embodiments wherein the amphiphile (A) is an amido amine according to one or more of formulae (15), (16), and (17), q is 1 or 2, depending on the presence of one or more of R3, R8, and R9.

[0158] In some embodiments wherein the amphiphile (A) is of the formula (16), the amphiphile (A) is the reaction product of (i) a N,N-dialkylaminoalkylamine having the general formula HN(R6)-R4-N(R1)(R2) with (ii) a first intermediate formed as the reaction product of one or more ethylenically unsaturated carboxylic acids or esters and an alkyl amine HN(R5)(R7). In such embodiments, the carboxylic acids or esters are an alkyl alkenoate (e.g., an alkyl methacrylate, an alkyl acrylate (for example, methyl acrylate)), an alkenoic acid (e.g., acrylic acid), or any combination thereof. In at least one embodiment, cocoylamine or oleylamine is first reacted with methyl acrylate and the reaction product is further reacted with a N,N-dialkylaminoalkylamine to form an amide. In such embodiments, the N,N-dialkylaminoalkylamine is selected from the group consisting of N,N- dimethylaminopropylamine, N,N-dibutylaminopropylamine, and pyrrolidine.

[0159] In some embodiments wherein the amphiphile (A) is of the formula (15) or (17), the amphiphile (A) is the reaction product of (i) an alkyl amine having the formula -N(R5)(R7) with (ii) a first intermediate formed as the reaction product of one or more ethylenically unsaturated carboxylic acids or esters (e.g., acrylates, methacrylates (for example, methyl acrylate)) and a N,N-dialkylamine to form an amide.

[0160] In some such embodiments, the N,N-dialkylamine has the general formula H[N(R6)- R4]P-N(R1)(R2). In some embodiments wherein p is 0, the N,N-dialkylamine is a secondary amine of the formula HN(R1)(R2), such as dimethylamine or dibutylamine. In some embodiments wherein p is 1 , the N,N-dialkylamine is an N,N- dialkylaminoalkylamine of the formula HN(R6)-R4-N(R1)(R2), such as N,N- dimethylaminopropylamine, N,N-dibutylaminopropylamine, pyrrolidine or the like. In such embodiments, the N,N-dialkylaminoalkylamine is reacted with methyl acrylate. The so formed intermediate reaction product can then be reacted with an alkyl amine of the formula -N(R5)(R7) to form an amide.

[0161] In some embodiments, the alkyl amine HN(R5)(R7) is a primary or secondary fatty amine derived from one or more fatty acids or fatty esters having from 6 to 24 carbon atoms or its esters. In some embodiments, the alkyl amine HN(R5)(R7) is derived from a fatty acid or ester selected from the group consisting of: com oil, canola oil, coconut oil, safflower oil, sesame oil, palm oil, cottonseed oil, soybean oil, olive oil, sunflower oil, hemp oil, wheat germ oil, palm kernel oil, vegetable oil, caprylic acid, capric acid, lauric acid, stearic acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, sapienic acid, elaidic acid, vaccenic acid, linoleic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, behenic acid, lignoceric acid, cerotic acid, and oleic acids (cis- and trans-). In some embodiments, the alkyl amine HN(R5)(R7) is a synthetic primary or secondary amine including, such as hexylamine, octylamine, dodecylamine, tridecylamine, tetradecylamine, N-methyldodecylamine, N- methyloctylamine, didodecylamine, and the like. In some embodiments, the alkyl amine HN(R5)(R7) is cocoylamine or oleylamine.

[0162] In some embodiments, the amide formed by the reaction of the N,N- dialkylaminoalkylamine H[N(R6)-R4]P-N(R1)(R2), the unsaturated carboxylic acid, and the alkyl amine HN(R5)(R7) is further reacted with (iii) one or more acids or with one or more alkylating agents to form the amphiphile (A). The one or more acids of formula HX may be an inorganic acid, such as a halide acid or a carboxylic acid, like formic acid, acetic acid propionic acid, acrylic acid, or methacrylic acid. The one or more alkylating agents may be a carbonate, a halide, a sulfate, an organic sulfonate, or a hydroxide. In such embodiments, R3and / or R8of the cation moiety may depend upon, among other factors, the alkyl group of the alkylating agent(s).

[0163] In some embodiments of the method disclosed herein, the linking moiety L of the amphiphile (A) comprises a structure of the formula (6). Such embodiments may be characterized as a reaction product of a N,N-dialkylaminoalkylamine of formula HN(R6)-R4-N(R1)(R2), wherein R1, R2, R4, and R6have the same meanings as given hereinabove, and a 1 ,2-epoxyalkane of formula (18) wherein R5has the meaning given above. In some embodiments, the 1 ,2- epoxyalkane is 1 ,2-epoxydecane, 1 ,2-epoxydodecane, 1 ,2-epoxytetradecane, 1 ,2-epoxyhexadecane, or 1 ,2-epoxyoctadecane. In some such embodiments, the reaction product of the N,N-dialkylaminoalkylamine and the 1 ,2-epoxyalkane may further be reacted with one or more acids and / or alkylating agents. The alkylating agent may include alkyl halides, alkyl sulfates, oxalates, carbonates, hydrocarbyl epoxides, and mixtures thereof. In some embodiments, the alkylating agent may be a sulfate, such as dimethyl sulfate. In some embodiments, the alkylating agent may be a halide, such as CH3CI. In some embodiments, the alkylating agent may be a carbonate, such as dimethyl carbonate. In some embodiments, the alkylating agent may be an epoxide, such as a hydrocarbyl epoxide, such as, for example, ethylene oxide, propylene oxide, butylene oxide, and the like. In some embodiments, the alkylating agent may be acrylic acid or methacrylic acid. In at least one embodiment, the alkylating agent is selected from the group consisting of methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, dimethyl sulfate, diethyl sulfate, and any combination thereof. In some embodiments wherein the alkyl group has at least 2 carbon atoms, the alkyl group is substituted with a hydroxyl group or a carboxyl group at the 2-position.

[0164] In some embodiments of the method disclosed herein, the linking moiety L of the amphiphile (A) may comprise one or more of structural elements (7a), (7b) and / or (7c). Such embodiments may be characterized as the reaction products of (i) a dicarboxylic acid substituted with a hydrocarbyl substituent R5with (ii) a nitrogen containing compound having, besides a group -N(R1)(R2), an oxygen or nitrogen atom capable of condensing with the dicarboxylic acid. The dicarboxylic acid may be an alkylsuccinic acid or its anhydride or an alkenylsuccinic acid or its anhydride. The nitrogen compound may be an N,N-dialkylaminoalkylamine having the structure H-[N(R6)-R4]P-N(R1)(R2) or a N,N-dialkylaminoalkanol having the structure HO-R4-N(R1)(R2), wherein R1, R2, R4, R6and p have the same meanings as given hereinabove.

[0165] The reaction product of the dicarboxylic acid and the N,N-dialkylaminoalkylamine may be an amide according to formula (7a) or (7b), or an imide according to formula (7c). The reaction product between the dicarboxylic acid and the N,N- dialkylaminoalkanol may be an ester according to formula (8a) or (8b) and will be similarly suited as amphiphile (A). In some embodiments, the reaction product of the dicarboxylic acid and the nitrogen containing compound may further be reacted with one or more acids and / or quaternizing agents suitable for converting the amino group -N(R1)(R2) to a quaternary nitrogen compound -N(R1)(R2)(R3)+X whereby the same acids and alkylating agents are the same as those described in the preceding embodiments.

[0166] In some embodiments of the method disclosed herein, the linking moiety L of the amphiphile (A) comprises a structure of formulae (9), (10a), (10b), (11 ), (12a) and (12b). Such methods use hydrate inhibitor compounds that may be characterized as unsymmetrically substituted dicarboxylic acid diamido ammonium compounds. These embodiments may be obtained by sequentially condensing a dicarboxylic acid with a fatty amine HN(R5)(R7) to give an intermediate amide and / or imide, followed by the reaction of the intermediate amide and / or imide with an N,N-dialkylaminoalkylamine of the structure H-[N(R6)-R4]P-N(R1)(R2). The reversed sequence of reaction steps will result in a similar product. In some embodiments, the dicarboxylic acid has from 4 to 14 or from 2 to 8 carbon atoms. In some embodiments, the dicarboxylic acid is further substituted by one or more hydroxyl, carboxyl, or carboxymethyl groups. In some embodiments, the dicarboxylic acid is succinic acid, and the linking moiety L is of the formula (9)). In some embodiments, the dicarboxylic acid is malic acid, and the linking moiety L is of the formula (10a) or (10b)). In some embodiments, the dicarboxylic acid is tartaric acid, and the linking moiety L is of the formula (11 ). In some embodiments, the dicarboxylic acid is citric acid, and the linking moiety L is of the formula (12a) or (12b). The thus obtained N,N-dialkylaminoalkylamide may be further reacted with an acid to form an ammonium salt or it may be quaternized with an alkylating agent whereby the same acids and alkylating agents are as described in the preceding embodiments. In at least one embodiment described herein, the at least one amphiphile (A) comprises a single amphiphile. In some embodiments described herein, the at least one amphiphile (A) comprises a mixture of two or more different amphiphiles. When the at least one amphiphile (A) is a mixture of different amphiphiles, the components may differ in their chemical and / or physicochemical properties, such as in the alkyl chain length, the branching of the lipophilic tail R5, the chain length of the alkyl residues R1and R2, the structure of the linking moiety L, and, if present, the nature of the anion. It is specifically contemplated that mixtures of the various amphiphiles of formulas (1 a) and (1 b) described herein may be used to provide the at least one amphiphile (A).

[0167] SURFACTANT (B)

[0168] In some embodiments disclosed herein, the at least one surfactant (B) comprises an imidazoline head group and a C9-C19 linear hydrocarbyl tail. As used herein, “imidazoline head group” can refer to a neutral imidazoline or to a cationic quaternary imidazolinium, or to their corresponding ring-opened structures.

[0169] In some embodiments, the at least one surfactant (B) comprises or consists of one or more selected from the group consisting of an imidazoline of the general formula (19a), a quaternary imidazolinium salt of the general formula (19b), and a quaternary imidazolinium salt of the general formula (19c),

[0170] (19a) (19b) (19c).

[0171] In some embodiments,

[0172] R11is an alkyl group having from 9 to 19 carbon atoms or is an alkenyl group having from 9 to 19 carbon atoms and 1 to 3 carbon-carbon double bonds; R12is an optionally substituted alkyl group having from 1 to 18 carbon atoms, or is a nitrogen-containing heteroaliphatic group;

[0173] R13is selected from the group consisting of an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, and a benzyl group; and

[0174] Y’ is an anion.

[0175] In some embodiments, R11has from 9 to 17, from 11 to 19, or from 11 to 17 carbon atoms. In some embodiments, R11is a linear or branched alkyl group. In at least one embodiment, R11is a linear alkyl group. In some embodiments, R11is an alkyl group derived from a saturated fatty acid. In some embodiments, R11is a linear or branched alkenyl group. In at least one embodiment, R11is a linear alkenyl group. In some embodiments, R11is an alkenyl group containing 1 carbon-carbon double bond or 2 carbon-carbon double bonds that are not conjugated to each other. In some embodiments, R11is selected from an alkenyl group having 17 carbon atoms and one carbon-carbon double bond, an alkenyl group having 17 carbon atoms and two carbon-carbon double bonds, and an alkenyl group having 17 carbon atoms and three carbon-carbon double bonds.

[0176] The surfactant component (B) may comprise a mixture of imidazoline / imidazolinium salts with varying R11groups. In this mixture, some R11groups are alkyl chains derived from saturated fatty acids, while others are alkenyl chains derived from unsaturated fatty acids. In such mixtures, the R11groups that are alkyl chains derived from saturated fatty acids may be present in an amount of from 5 to 60 mol- %, from 15 to 60 mol-%, from 20 to 60 mol-%, from 5 to 40 mol-%, from 15 to 40 mol-%, from 20 to 40 mol-%, from 5 to 20 mol-%, from 15 to 20 mol-%, from 5 to 10 mol-%, or from 1 to 10 mol-%, based on the total amount of imidazolines / imidazolinium salts in the mixture.

[0177] In some embodiments, R12is an alkyl group having from 1 to 16, from 1 to 12, from 1 to 6, from 2 to 16, from 2 to 12, or from 2 to 6 carbon atoms. In some embodiments, R12is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and dodecyl. In some embodiments, R12is a hydroxyalkyl group. In at least one embodiment, R12is a hydroxyalkyl group having from 1 to 16, from 1 to 12, from 1 to 6, from 2 to 16, from 2 to 12, from 2 to 6, or from 2 or 3 carbon atoms. In some embodiments, R12is selected from the group consisting of hydroxyethyl and hydroxypropyl. In at least one embodiment, R12is a hydroxyethyl group.

[0178] In some embodiments wherein R12is a heteroaliphatic group, R12is an aminoalkylene group, a polyaminoalkylene group, or an ammoniumalkylene group having from 2 to 20 carbon atoms and from 1 to 10 nitrogen atoms. In some such embodiments, one or more of the nitrogen atoms are alkylated or acylated. In some embodiments, the aminoalkylene, polyaminoalkylene, or ammoniumalkylene group is characterized as an aliphatic chain with single carbon atoms replaced by nitrogen atoms. In some embodiments, the polyaminoalkylene, polyaminoalkylene, or ammoniumalkylene group is linear or branched.

[0179] In some embodiments, R12is an aminoalkylene or polyaminoalkylene group of the formula (20a) or is an ammoniumalkylene group of the structural formula (20b),

[0180] -{(CH2)r-[NR14-(CH2)s]t-NR15R16} (20a)

[0181] -{(CH2)r-[NR14R18-(CH2)s]t-NR15R16R18}v+vY’ (20b).

[0182] In some embodiments,

[0183] R14is hydrogen or an optionally substituted hydrocarbyl residue having from 1 to 20 carbon atoms;

[0184] R15is hydrogen or an optionally substituted hydrocarbyl residue having from 1 to 20 carbon atoms;

[0185] R16is selected, independently from R15, from hydrogen, an optionally substituted hydrocarbyl residue having 1 to 20 carbon atoms, and an acyl group having the formula -C(=O)-R17, with the proviso that R15and R16together may form a 5- or 6-membered ring,

[0186] R17is hydrogen or a C1-C18 hydrocarbyl group;

[0187] R18is hydrogen, an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, or a benzyl group; r and s are each, independently, 2 or 3; t is 0 or an integer from 1 to 10; v is 0 or an integer between 1 and 11 ; and

[0188] Y’ is an anion.

[0189] In some embodiments, R12is an aminoalkylene group or an N-substituted aminoalkylene. In such embodiments, t is 0. In at least such one embodiment, r is 2. In some embodiments, R12is selected from the group consisting of aminoethyl, aminopropyl, N-methyl aminoethyl, N-ethyl aminoethyl, N-propyl aminoethyl, N- butyl aminoethyl, N,N-dimethyl aminoethyl, N,N-diethyl aminoethyl, N,N-dipropyl aminoethyl, and N, N-dibutyl aminoethyl.

[0190] In some embodiments, R12is a polyaminoalkylene group. In some such embodiments, t is an integer from 1 to 6 or from 1 to 4. In some such embodiments, t is 1 , 2, or 3. In at least one embodiment, r and s are both 2. In some embodiments, R12is selected from the group consisting of N-(2-aminoethyl) aminoethyl, N-(2- aminoethyl)aminopropyl, and higher homologues thereof.

[0191] In some embodiments wherein R12is an aminoalkylene group, a polyaminoalkylene group or an ammoniumalkylene group, R14is selected from the group consisting of hydrogen and hydrocarbyl groups having from 1 to 6 or from 1 to 3 carbon atoms. In at least one embodiment, R14is an alkyl group. In some such embodiments, the alkyl group is selected from the group consisting of methyl, ethyl, and propyl. In at least one embodiment, R14is hydrogen.

[0192] In some embodiments, R15and R16are, independently, selected from the group consisting of hydrogen and an optionally substituted hydrocarbyl group. In some embodiments, R15and R16are the same. In some embodiments, R15and R16are different. In some embodiments, at least one of R15and R16is an optionally substituted hydrocarbyl group having from 1 to 14, from 1 to 6, or from 1 to 4 carbon atoms. In some embodiments, at least one of R15and R16is an alkyl group. In some embodiments, at least one of R15and R16is an alkyl group substituted with a hydroxyl group. In some embodiments, at least one of R15and R16is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and hydroxyethyl. In at least one embodiment, R15is hydrogen and R16is hydroxyethyl. In some embodiments, R15is hydrogen and R16is an acyl group. In some such embodiments, R16is an acyl group having from 1 to 12, from 1 to 6, or from 1 to 4 carbon atoms (including the carbonyl carbon atom). In some embodiments, R16is an acyl group derived from acetic acid, propionic acid, butyric acid, acrylic acid, or methacrylic acid.

[0193] In some embodiments wherein the at least one surfactant (B) includes a salt of the formula (19b) or (19c), R13is an alkyl group having from 1 to 4 or from 1 or 2 carbon atoms. In some embodiments, R13is a hydroxyalkyl group having 2 or 3 carbon atoms. In at least one embodiment, R13is a hydroxyalkyl group having 2 carbon atoms. In some embodiments, R13is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and hydroxyethyl. In at least one embodiment R13is selected from the group consisting of methyl, ethyl, and hydroxyethyl. In at least one embodiment R13is ethyl. In some embodiments one or both of R12and R13are hydroxyalkyl.

[0194] In some embodiments, the imidazoline of formula (19a) is formed by the reaction of a fatty acid (i) with an N-substituted ethylene diamine (ii) under dehydrating conditions.

[0195] In some embodiments, the fatty acid (i) and the alkylene polyamine (ii) are reacted in a molar ratio of from 5: 1 to 1 :5, from 2:1 to 1 :2, from 1.2 :1 to 1 : 1 .2, from 5: 1 to 1 :2, from 5:1 to 1 :1.2, from 2:1 to 1 :5, from 2:1 to 1.2, from 1.2:1 to 1 :5, or from 1.2:1 to 1 :2. For alkylene polyamines (ii) having 4 or more nitrogen atoms, the molar ratio of the fatty acid (i) to the alkylene polyamine (ii) may be doubled in order to obtain diamides and / or bis-imidazolines.

[0196] In some embodiments, the fatty acid (i) has from 10 to 20 or from 12 to 18 carbon atoms. In some embodiments, the fatty acid is selected from the group consisting of oleic acid, linoleic acid, linolenic acid, and mixtures thereof. In some embodiments, the fatty acid is selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof. In some embodiments, the fatty acid is selected from the group consisting of coconut oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid, and tallow fatty acid. In at least one embodiment, the fatty acid is tall oil fatty acid.

[0197] In some embodiments, the N-substituted ethylene diamine (ii) is a polyamine having three or more amino groups. In some embodiments, the N-substituted ethylene diamine (ii) is a polyamine having from 3 to 12 or from 3 to 6 amino groups. In some embodiments, the N-substituted ethylene diamine (ii) is a polyamine having 3, 4, 5, or 6 amino groups. In some embodiments, the N-substituted ethylene diamine (ii) is selected from the group consisting of diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, and higher homologues thereof, such as heavy polyamines or polyamine bottoms. Heavy polyamines and polyamine bottoms are byproducts of polyamine manufacturing, typically produced through the reaction of ethylene dichloride with ammonia. These compounds are obtained by stripping a polyamine mixture to remove lower molecular weight polyamines and volatile components, leaving behind a residue of higher molecular weight, more complex structures known as polyamine bottoms.

[0198] In some embodiments, the N-substituted ethylene diamine (ii) is a N-alkylated ethylene diamine selected from the group consisting of N'-methylethane-1 ,2- diamine, N'-ethylethane-1 ,2-diamine, N'-butylethane-1 ,2-diamine, N'-octadecylethane-1 ,2-diamine, 2-(2-aminoethylamino)ethanol

[0199] N'-[2-(methylamino)ethyl]ethane-1 ,2-diamine, N’-[2-(ethylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(butylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(dimethylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(diethylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(dibutylamino)ethyl]ethane-1 ,2-diamine, 2-[2-(2-aminoethylamino)ethylamino]ethanol, and mixtures thereof.

[0200] In some embodiments, the N-substituted ethylene diamine (ii) has the general formula (21 )

[0201] H2N-(CH2)2-NH-R12(21 ) wherein R12has the meanings given hereinabove. In some such embodiments, the N-substituted ethylene diamine (ii) is an amino alkylethanolamine, such as aminoethylethanolamine.

[0202] In some embodiments, the N-substituted ethylene diamine of the formula (21 ) contains a cyclic structure. In such embodiments, R15and R16, together with the nitrogen atom to which they are attached, form a 5- or 6-membered ring. In some such embodiments, the 5- or 6-membered ring contains one further nitrogen atom. In some such embodiments, the - or 6-membered ring is an imidazoline or a piperazine structure.

[0203] In some embodiments, the imidazoline formed by the reaction of the fatty acid (i) with the N-substituted ethylene diamine (ii) is further reacted with a quaternizing agent (iii). The quaternizing agent may convert some of or all the secondary and tertiary amino groups to quaternary ammonium groups. The degree of quaternization depends on the molar ratio of imidazoline to quaternizing agent and the reaction conditions. In some embodiments, the imidazoline is quaternized once to give an imidazolinium salt.

[0204] In some embodiments, the quaternizing agent is an alkylating agent. In some embodiments, the quaternizing agent is an alkylhalogenide, such as methylchloride, ethylchloride, propylchloride, butylchloride, benzylchloride, methylbromide, ethylbromide, propylbromide, butylbromide, benzylbromide; a dialkylsulfate, such as dimethylsulfate, diethylsulfate, dipropylsulfate and dibutylsulfate; or a dialkylcarbonate, such as dimethylcarbonate and diethylcarbonate. In at least one embodiment, the quaternizing agent does not contain a halogenide.

[0205] In some embodiments, the imidazoline of the formula (19a) is reacted with a quaternizing agent. In some embodiments, the quaternizing agent adds substituent R13to the nitrogen atom in the 1 -position of the imidazoline of formula (19a) to provide the imidazolinium salt of formula (19b) or to the nitrogen atom in the 3- position of the imidazoline of formula (19a) to provide the imidazolinium salt of formula (19c). In some embodiments, Y’ is selected from the group consisting of halides, sulfate, organic sulfates, carbonate, organic carbonates, phosphate, nitrate, and carboxylates, and any mixture thereof. In at least one embodiment, Y’ is sulfate. In some embodiments, Y’ is a halide selected from the group consisting of chloride, bromide, and iodide. In some embodiments, Y’ is an organic sulfate selected from the group consisting of CH3SO4; C2H5SO4 , C3H7SO4; and C4HgSO4’. In some embodiments, Y’ is an organic carbonate selected from the group consisting of CH3- O-COO and CH2H5-O-COO’. In some embodiments, Y’ is a carboxylate selected from the group consisting of acetate, propionate, butylate, acrylate, and methacrylate. In at least one embodiment, Y’ is selected from the group consisting of Cl CHsSCM’, C2H5SO4-, CsHySCM’, and any mixture thereof. In at least one embodiment, Y’ is selected from the group consisting of CHsSCM’, C2HsSO4’, C3H7SO4; and any mixture thereof. In some embodiments where R12contains one or more quaternary ammonium groups, i.e. where groups R18are present, the number “v” of anions Y’ is equivalent to the number of ammonium groups.

[0206] In various embodiments, the at least one surfactant (B) includes an imidazoline of the formula (19a) formed by the reaction of tall oil fatty acid with aminoethylethanolamine or tetraethylenepentamine.

[0207] In various embodiments, the at least one surfactant (B) comprises or consists of a quaternary imidazolinium salt of the formula (19b) or (19c) formed by the reaction of tall oil fatty acid with aminoethylethanolamine or tetraethylenepentamine, followed by quaternization with a dialkylsulfate selected from the group consisting of dimethylsulfate, diethylsulfate, dipropylsulfate and dibutylsulfate.

[0208] In various embodiments, the at least one surfactant (B) comprises or consists of an imidazoline of the formula (19a), wherein

[0209] R11is an alkenyl group having 17 carbon atoms and 1 or 2 carbon-carbon double bonds; and

[0210] R12is a hydroxyethyl group.

[0211] In various embodiments, the at least one surfactant (B) comprises or consists of a quaternary imidazolinium salt of the formula (19b) or (19c), wherein R11is an alkenyl group having 17 carbon atoms and 1 or 2 carbon-carbon double bonds;

[0212] R12is a hydroxyethyl group;

[0213] R13is ethyl.

[0214] In various embodiments, the at least one surfactant (B) comprises or consists of one or more selected from the group consisting of 2-oleyl-N-methyl imidazoline quaternized with methylchloride, 2-oleyl-N-hydroxyethyl imidazoline quaternized with methylbromide, 2-oleyl-N-hydroxyethyl imidazoline quaternized with diethylsulfate, 2-oleyl-N-butyl-imidazoline quaternized with diethylsulfate, 2-linoleyl-N hydroxyethyl imidazoline quaternized with dimethylsulfate, 2-tallyl-N-N’-aminoethyl imidazoline with methylchloride.

[0215] Here, too, it is specifically contemplated that the at least one surfactant (B) may be provided as a mixture of imidazoline / imidazolium surfactants, for example, as described in general formulas (19a), (19b) and (19c).

[0216] Moreover, the person of ordinary skill in the art appreciates that imidazoline and imidazolium surfactants described here with respect to cyclic ring structures can exist in an equilibrium with a ring-opened form, especially depending on pH. While the imidiazolines and imidazoliums are described generally here with respect to the cyclic form, such descriptions as used herein also encompass the corresponding ring-opened form.

[0217] In some embodiments disclosed herein, the amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) range of from 95:5 to 5:95, from 85:15 to 15:85, from 75:25 to 25:75, from 70:30 to 30:70, from 65:35 to 35:65, from 60:40 to 40:60, or from 55:45 to 45:55. In some embodiments disclosed herein, the amphiphile (A) and the at least one surfactant (B) are present in a weight- to-weight ratio (A):(B) range of from 10:1 to 1 :10, from 8:3 to 3:8, from 7:4 to 4:7, from 6:5 to 5:6, from 5:4 to 4:5, from 5:3 to 3:5, from 3:1 to 1 :3, from 4:1 to 1 :4, from 5:2 to 2:5, from 3:2 to 2:3, or from 2:1 to 1 :2. However, the present inventors have noted that in many embodiments, relatively less surfactant (B) and relatively more amphiphile (A) can be used. For example, in various embodiments, the amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) range of from 95:5 to 50:50, e.g., from 95:5 to 60:40, or from 95:5 to 70:30, or from 90: 10 to 50:50, or from 90: 10 to 60:40, or from 90: 10 to 70:30.

[0218] In some embodiments disclosed herein, the amphiphile (A) is present in an amount of from 5 to 95 wt.-%, from 5 to 85 wt.-%, from 5 to 75 wt.-%, from 5 to 65 wt.-%, from 5 to 60 wt.-%, from 5 to 55 wt.-%, from 5 to 50 wt.-%, from 5 to 45 wt.-%, from 5 to 40 wt.-%, from 5 to 35 wt.-%, from 5 to 30 wt.-%, from 5 to 25 wt.-%, from 10 to 95 wt.-%, from 10 to 85 wt.-%, from 10 to 75 wt.-%, from 10 to 65 wt.-%, from 10 to 60 wt.-%, from 10 to 55 wt.-%, from 10 to 50 wt.-%, from 10 to 45 wt.-%, from 10 to 40 wt.-%, from 10 to 35 wt.-%, from 10 to 30 wt.-%, from 10 to 25 wt.-%,15 to 95 wt.-%, from 15 to 85 wt.-%, from 15 to 75 wt.-%, from 15 to 65 wt.-%, from 15 to 60 wt.-%, from 15 to 55 wt.-%, from 15 to 50 wt.-%, from 15 to 45 wt.-%, from 15 to 40 wt.-%, from 15 to 35 wt.-%, from 15 to 30 wt.-%, from 15 to 25 wt.-%, from 20 to 95 wt.-%, from 20 to 85 wt.-%, from 20 to 75 wt.-%, from 20 to 65 wt.-%, from 20 to 60 wt.-%, from 20 to 55 wt.-%, from 20 to 50 wt.-%, from 20 to 45 wt.-%, from 20 to 40 wt.-%, from 20 to 35 wt.-%, from 20 to 30 wt.-%, from 20 to 25 wt.-%,from 25 to 95 wt.-%, from 25 to 85 wt.-%, from 25 to 75 wt.-%, from 25 to 65 wt.-%, from 25 to 60 wt.-%, from 25 to 55 wt.-%, from 25 to 50 wt.-%, from 25 to 45 wt.-%, from 25 to 40 wt.-%, from 25 to 35 wt.-%, or from 25 to 30 wt.-%, based on the combined weights of (A) and (B).

[0219] In some embodiments disclosed herein, the at least one surfactant (B) is present in an amount of 5 to 95 wt.-%, from 5 to 85 wt.-%, from 5 to 75 wt.-%, from 5 to 65 wt.- %, from 5 to 55 wt.-%, from 5 to 50 wt.-%, from 5 to 45 wt.-%, from 5 to 40 wt.-%, 15 to 95 wt.-%, from 15 to 85 wt.-%, from 15 to 75 wt.-%, from 15 to 65 wt.-%, from 15 to 55 wt.-%, from 15 to 50 wt.-%, from 15 to 45 wt.-%, from 15 to 40 wt.-%, 20 to 95 wt.-%, from 20 to 85 wt.-%, from 20 to 75 wt.-%, from 20 to 65 wt.-%, from 20 to 55 wt.-%, from 20 to 50 wt.-%, from 20 to 45 wt.-%, from 20 to 40 wt.-%, 25 to 95 wt.-%, from 25 to 85 wt.-%, from 25 to 75 wt.-%, from 25 to 65 wt.-%, from 25 to 55 wt.-%, from 25 to 50 wt.-%, from 25 to 45 wt.-%, from 25 to 40 wt.-%, 30 to 95 wt.- %, from 30 to 85 wt.-%, from 30 to 75 wt.-%, from 30 to 65 wt.-%, from 30 to 55 wt.- %, from 30 to 50 wt.-%, from 30 to 45 wt.-%, or from 30 to 40 wt.-%, based on the combined weights of (A) and (B).

[0220] FURTHER SURFACTANT (C)

[0221] In some embodiments disclosed herein, a system containing hydrocarbons and water is brought into contact with an amphiphile (A), at least one surfactant (B), and at least one further surfactant (C) (hereinafter, alternatively, “surfactant (C)” or “(C)”). Compared to compositions without surfactant (C), those containing it have a lower surface tension. Accordingly, the presence of surfactant (C) enhances the performance of (A) and (B), allowing for reduced treatment rates beyond just using (A) and (B) together. Surfactant (C) can also improve secondary properties, potentially eliminating the need for additional treatments to address issues like emulsion formation.

[0222] In some embodiments wherein the system containing hydrocarbons and water is brought into contact with an amphiphile (A), at least one surfactant (B), and at least one further surfactant (C), the at least one further surfactant (C) is present in an amount of from 1 to 25 wt.-%, from 5 to 25 wt.-%, from 10 to 25 wt.-%, from 12 to 25 wt.-%, from 14 to 25 wt.-%, from 16 to 25 wt.-%, from 18 to 25 wt.-%, from 20 to 25 wt.-%, from 1 to 20 wt.-%, from 5 to 20 wt.-%, from 10 to 20 wt.-%, from 12 to 20 wt.-%, from 14 to 20 wt.-%, from 16 to 20 wt.-%, from 18 to 20 wt.-%, from 1 to 18 wt.-%, from 5 to 18 wt.-%, from 10 to 18 wt.-%, from 12 to 18 wt.-%, from 14 to 18 wt.-%, from 16 to 18 wt.-%, from 1 to 16 wt.-%, from 5 to 16 wt.-%, from 10 to 16 wt.-%, from 12 to 16 wt.-%, or from 14 to 16 wt.-%, based on the combined weights of(A), (B), and (C). In some embodiments, the at least one further surfactant (C) is present in an amount of at least 15 wt.-%, at least 20 wt.-%, at least 25 wt.-%, at least 30 wt.-%, at least 35 wt.-%, at least 40 wt.-%, or at least 50 wt.-% of the combined weights of (A) and (B). In some embodiments, the amphiphile (A) and the at least one further surfactant (C) are present in a weight-to-weight ratio (A):(C) of from 1 :1 to 4:1 , from 1.5:1 to 4:1 , from 1 :1 to 3:1 , from 1.5:1 to 3:1 , from 1 :1 to 2:1 , or from 1.5:1 to 2:1. In embodiments, the at least one further surfactant (C) is selected from the group consisting of anionic, nonionic, zwitterionic (amphoteric), and surfactants. In embodiments, the at least one further surfactant (C) is different from the amphiphile (A) and the at least one surfactant (B).

[0223] In some embodiments, the at least one further surfactant (C) contains one or more hydrophobic groups, such as alkenyl, cycloalkenyl, alkyl, cycloalkyl, aryl, alkyl / aryl, or more complex aryl moieties. In some such embodiments, the hydrophobic groups contain from 8 to 22, from 10 to 20, or from 12 to 18 carbon atoms. In some embodiments, the at least one further surfactant (C) contains one or more hydrophilic moieties, which may be nonionic, anionic, cationic, or amphoteric. In some embodiments, the at least one further surfactant (C) contains one or more additional hydrophobic groups, such as polysiloxane or polyoxyalkylene groups.

[0224] In some embodiments, the at least one further surfactant (C) is a water-soluble (forms a homogeneous solution in water) or water-dispersible (forms a stable suspension or dispersion when mixed with water) compound having a cationic portion, an anionic portion, or both. In some embodiments comprising a cationic portion, the at least one further surfactant (C) includes a nitrogen atom and either one or two alkyl groups each having an average of from 8 to 22 carbon atoms. In some embodiments containing an anionic portion, the at least one further surfactant (C) includes an anion that confers water solubility. In such embodiments, the anion that confers water-solubility is a formate, an acetate, a lactate, a tartrate, a citrate, a chloride, a nitrate, a sulfate, or an alkyl sulfate ion having up to 4 carbon atoms, such as a higher alkyl sulfate or organic sulfonate.

[0225] In some embodiments disclosed herein, the at least one further surfactant (C) comprises or consists of a cationic surfactant. In some such embodiments, the at least one further surfactant (C) comprises or consists of an N-alkyl pyridinium salt, wherein the alkyl group has an average of from 8 to 22 or from 10 to 20 carbon atoms. Other similarly alkylated heterocyclic salts, such as N-alkyl isoquinolinium salts, may also be used. In some embodiments, the at least one further surfactant (C) comprises or consists of alkylaryl dialkylammonium salts, wherein the alkylaryl group is an alkyl benzene group having an average of from 8 to 22 or 10 to 20 carbon atoms and the other two alkyl groups have from 1 to 4 carbon atoms. In some embodiments, the at least one further surfactant (C) comprises or consists of alkylammonium salts having one or at most two long aliphatic chains per molecule and two or three short chain alkyl groups, wherein the long aliphatic chains have an average of from 8 to 20 or from 12 to 18 carbon atoms each and the short chain alkyl groups have from 1 to 4 carbon atoms. In some embodiments, the at least one further surfactant (C) comprises or consists of alkyl phosphonium or hydroxyalkyl phosphonium salts having one alkyl group of from 8 to 20 carbon atoms and three alkyl or hydroxyalkyl groups of from 1 to 4 carbon atoms.

[0226] In some embodiments disclosed herein, the at least one further surfactant (C) comprises or consists of a non-ionic surfactant. In embodiments, the at least one further surfactant (C) comprises or consists of one or more selected from the group consisting of polyalkoxylated alcohols, polyalkoxylated mercaptans, alkylpolyglucosides, polyalkoxylated carboxylic acids, polyalkoxylated amines, polyalkoxylated alkylolamides, polyalkoxylated alkylphenols, polyalkoxylated esters, polyalkoxylated tertiary acetylenic glycols, glucamines, glucamine alkoxylates, glucamides, and glucamide alkoxylates. In this context, “alkoxylated” refers to compounds modified by the addition of alkoxy groups, particularly ethyleneoxy and / or propyleneoxy groups. In various embodiments, the at least one further surfactant (C) comprises or consists of one or more polyalkoxylated alkyl esters (i.e., “alkyl-capped” polyalkoxylated carboxylic acids)., such as polyalkoxylated methyl esters. In embodiments, alkoxylated compounds include those having an alkyl or alkenyl group containing from 8 to 22 carbon atoms and up to 20 ethyleneoxy and / or propyleneoxy groups, such as ethoxylated and / or propoxylated analogues of non-ionic surfactants.

[0227] In embodiments, the at least one further surfactant (C) comprises or consists of one or more selected from the group consisting of polyethoxylated glyceryl esters, polyethoxylated sorbitan esters, and polyethoxylated phosphate esters. In embodiments, the at least one further surfactant (C) comprises or consists of a partial ester of a polyhydric compound having 3 or more hydroxyl groups with fatty acids, wherein the polyhydric compound is selected from the group consisting of glycerol, trimethylolpropane, erythritol, pentaerythritol, sorbitan, sorbitol, and xylitol. In embodiments, the at least one further surfactant (C) comprises or consists of one or more selected from the group consisting of polyoxypropylene / polyethylene oxide block copolymers, polyoxybutylene / polyoxyethylene copolymers, and polyoxybutylene / polyoxypropylene copolymers. These copolymers may be endcapped with an alkyl group, such as a methyl or benzyl group, to reduce foaming tendency. In embodiments, the at least one further surfactant (C) comprises or consists of an alkanolamide of a mono or di-lower alkanolamine having from 8 to 22 carbon atoms, such as coconut monoethanolamide.

[0228] In some embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (22):

[0229] R19-Y-(AO)w-R20(22) wherein

[0230] R19is an alkyl or alkenyl group having 8 to 18 carbon atoms;

[0231] Y is -O-, -N(R21)-, -C(=O)-O- or -C(=O)-N(R21)-;

[0232] A is a Ci to C4 alkylene group;

[0233] R20is hydrogen, an alkyl group having from 1 to 5 carbon atoms, a benzyl group, or -C(O)-R22;

[0234] R21is hydrogen, an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, or a group of formula -(AO)w-R20;

[0235] R22is a Ci to Cs-hydrocarbyl group; and w is an integer between 1 and 25.

[0236] When Y is -O-, the at least one compound according to formula (22) is an alkoxylated fatty alcohol. When Y is -N(R21)-, the at least one compound according to formula (22) is an alkoxylated fatty amine. When Y is -C(=O)-O-, the at least one compound according to formula (22) is an alkoxylated fatty acid. When Y is -C(=O)- N(R21)-, the at least one compound according to formula (22) is an alkoxylated fatty acid amide. The terms “alkoxylated fatty alcohol”, “alkoxylated fatty amine”, “alkoxylated fatty acid” and “alkoxylated fatty acid amide” encompass the direct alkoxylation products of fatty alcohols, fatty acids, and fatty amines wherein R20is hydrogen, as well as the end-capped derivatives thereof, such as esters and ethers, where R20is an alkyl group. The fatty alcohol, the fatty acid, and the fatty amine being the basis for alkoxylation may be of synthetic origin or may be derived from renewable sources, such as corn oil, canola oil, coconut oil, cottonseed oil, safflower oil, sesame oil, sunflower oil, palm oil, soybean oil, olive oil, hemp oil, wheat germ oil, palm kernel oil, tallow fat, and / or hardened tallow fat.

[0237] In embodiments, the at least one further surfactant (C) comprises or consists of at least one alkoxylated fatty alcohol according to formula (22). In some embodiments, the at least one alkoxylated fatty alcohol is a polyalkoxylated Cs-Cis fatty alcohol. Fatty alcohol alkoxylates are accessible, for instance, by alkoxylation of fatty alcohols. In some embodiments, the at least one further surfactant (C) comprises or consists of at least one end-capped fatty alcohol alkoxylate ( / .e., an alkoxylated fatty ether). In such embodiments, R20is an alkyl group, such as methyl, ethyl, or other C1-C5 alkyl. End-capped fatty alcohol alkoxylates are accessible, for instance, by alkoxylation of fatty ethers. Alkoxylation can be achieved using an insertion catalyst.

[0238] In embodiments, the at least one further surfactant (C) comprises or consists of at least one alkoxylated fatty amine according to formula (22). In some embodiments, a fatty primary amine is alkoxylated to provide an alkoxylated fatty amine according to formula (22) wherein R21is H. In some embodiments, a fatty secondary amine is alkoxylated to provide an alkoxylated fatty amine according to formula (22) wherein R21is an alkyl or alkenyl group. In some such embodiments, R21is a linear or branched alkyl or alkenyl group having from 5 to 18, from 8 to 16, from 10 to 14 carbon atoms, from 5 to 16, from 5 to14, from 8 to 18, from 8 to 14, from 10 to 18, or from 10 to 16 carbon atoms. In such embodiments, the alkyl or alkenyl group may be linear or branched. Alkyl groups are saturated and alkenyl groups contain one or two double bonds. In some embodiments, the alkyl or alkenyl group is selected from the group consisting of methyl, ethyl, octyl, 2-ethyl hexyl, iso-nonyl, decyl, isoundecyl, dodecyl, iso-tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, and oleyl. In embodiments, the at least one further surfactant (C) comprises or consists of a mixture of compounds according to formula (22), wherein R21represents alkyl and / or alkenyl groups of varying chain lengths within the specified range. In embodiments, R21and R19are the same. In embodiments R21and R19are different. In at least one embodiment, R21and R19are the same.

[0239] In embodiments, the at least one further surfactant (C) comprises or consists of at least one alkoxylated fatty acid according to formula (22). Fatty acid alkoxylates are accessible, for instance, by alkoxylation of fatty acids. In some such embodiments, R20is H. In embodiments, the at least one further surfactant (C) comprises or consists of at least one end-capped fatty acid alkoxylate ( / .e., an alkoxylated fatty ester). In such embodiments, R20is an alkyl group, such as methyl, ethyl, or other C1-C5 alkyl. In at least one embodiment, the at least one further surfactant (C) comprises or consists of at least one fatty acid alkoxylate end-capped with a methyl group. End-capped fatty acid alkoxylates are accessible, for instance, by alkoxylation of fatty acid esters, such as by ethoxylation of fatty acid methyl esters. Alkoxylation can be achieved using an insertion catalyst.

[0240] In embodiments, the at least one further surfactant (C) comprises or consists of at least one alkoxylated fatty amide according to formula (22). In some embodiments, the alkyoxylated fatty acid amide is a tertiary amide wherein R21is an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 18 carbon atoms, or a group of formula -(AO)w-R20. In at least one embodiment, R21is an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, or butyl. In at least one embodiment, R21is a group of the formula -(AO)w-R20.

[0241] In embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (22) wherein R19is an alkyl or alkenyl group having from 8 to 16, from 10 to 14, from 8 to 14, from 10 to 18, from 10 to 16, from 13 to 20, from 13 to 19, from 15 to 20, or from 15 to 19 carbon atoms. In such embodiments, the alkyl or alkenyl group may be linear or branched. Alkyl groups are saturated and alkenyl groups contain one or two double bonds. In some embodiments, the alkyl or alkenyl group is selected from the group consisting of octyl, 2-ethyl hexyl, iso-nonyl, decyl, iso-undecyl, dodecyl, iso-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octenyl, 2-ethylhexenyl, iso-nonenyl, decenyl, iso-undecenyl, dodecenyl, iso-tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and oleyl. In embodiments, the at least one further surfactant (C) comprises or consists of a mixture of compounds according to formula (22), wherein R19represents alkyl and / or alkenyl groups of varying chain lengths within the specified range.

[0242] In some embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (22) wherein R20is -C(=O)-R22. In some embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (21 ) wherein R20is an alkyl group having from 1 to 5 carbon atoms or a benzyl group. In some embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (22) wherein R20is hydrogen. In some embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (22) wherein R20is a linear or branched alkyl group having from 1 to 4 carbon atoms. In embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (22) wherein R20is selected from the group consisting of methyl, ethyl, propyl, n-butyl, sec-butyl, and tert-butyl. In at least one embodiment, R20is methyl.

[0243] In embodiments, the at least one further surfactant (C) comprises or consists of at least one compound of the formula (22) wherein A is an alkylene group having 2 or

[0244] 3 carbon atoms. In such embodiments, the group -(AO)w- is derived from an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or any mixture thereof. In at least one embodiment, the group -(AO)w- is derived from ethylene oxide. In embodiments, the degree of alkoxylation w is from 2 to 20, from

[0245] 4 to 15, from 1 to 20, from 1 to 15, from 2 to 25, from 2 to 15, from 4 to 25, or from 4 to 20. In some embodiments, the distribution of the alkoxymers is broad, meaning the number of alkylene oxide units per molecule varies widely, yielding a wide molecular weight range as in conventional base-catalyzed products. In some embodiments, the distribution of the alkoxymers is tight, meaning most molecules contain a similar number of repeating units, such narrow distributions typically being obtained with a narrow-range catalyst.

[0246] In some embodiments, the at least one further surfactant (C) comprises or consist of an amphoteric surfactant. In some such embodiments, the amphoteric surfactant is a betaine, such as of the formula (R23)3N+CH2COO_, wherein each R23may be the same or different and is an alkyl, cycloalkyl, alkenyl or alkaryl group. In some such embodiments, at least one R23has an average of from 8 to 20 carbons of an aliphatic nature and each other R23has an average of from 1 to 4 carbon atoms.

[0247] In some embodiments, the amphoteric surfactant is selected from one or more of the group consisting of quaternary imidazolines, alkyl amine ether sulfates, sulfobetaines, and other quaternary amine or quaternized imidazoline sulfonic acids and salts thereof. In some embodiments, the amphoteric surfactant is a zwitterionic surfactant, such as an N-alkyl taurine, a carboxylate amidoamine, or an amido acid. In such embodiments, the zwitterionic surfactant includes hydrocarbon groups capable of conferring surfactant properties. In some embodiments, the amphoteric surfactant is selected from one or more of the group consisting of 2-tallow alkyl, 1- tallow amido alkyl, 1 -carboxymethyl imidazoline and 2-coconut alkyl N- carboxymethyl 2 (hydroxyalkyl) imidazoline. In general, any water soluble amphoteric or zwitterionic surfactant compound that comprises a hydrophobic portion, including an alkyl or alkenyl group of from 8 to 20 carbon atoms, and a hydrophilic portion, containing an amine or quaternary ammonium group and a carboxylate, sulfate or sulfonic acid group, may be included in the at least one further surfactant (C).

[0248] In some embodiments, the amphoteric surfactant is an amine oxide. In some such embodiments, the amine oxide contains one or two alkyl groups of from 8 to 22 carbon atoms, and the remaining substituent or substituents are lower alkyl groups, such as alkyl groups of from 1 to 4 carbon atoms, or benzyl groups. In some embodiments, the amphoteric surfactant is a surfactant that is effective as a wetting agent. Typically, such surfactants are effective at lowering the surface tension between water and a hydrophobic solid surface. Surfactants are preferred which do not stabilize foams to a substantial extent.

[0249] In some embodiments, the at least one further surfactant (C) is of the formula (23) wherein

[0250] Ra is a linear or branched, saturated or unsaturated hydrocarbon residue having from 5 to 21 or from 7 to 13 carbon atoms, and

[0251] Rb is an alkyl residue having from 1 to 4 carbon atoms.

[0252] In another preferred embodiment, the at least one further surfactant (C) is of the formula (24), (25), or (26):

[0253] 24 25 26 wherein Ra and Rb have the same meanings as given hereinabove.

[0254] In some embodiments, the at least one further surfactant (C) comprises or consists of an anionic surfactant. The anionic surfactant may comprise or consist of an at least sparingly water-soluble salt of sulfonic or mono-esterified sulfuric acids, e.g. an alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, olefin sulfonate, alkane sulfonate, alkylphenol sulfate, alkylphenol ether sulfate, alkylethanolamide sulfate, alkylethanolamidether sulfate, or alpha sulfo fatty acid or its ester, each having at least one alkyl or alkenyl group with from 8 to 22 or from 10 to 20 aliphatic carbon atoms.

[0255] Other possible anionic surfactants include alkyl sulfosuccinates such as sodium dihexylsulfosuccinate, alkyl ether sulfosuccinates, alkyl sulfosuccinamates, alkyl ether sulfosuccinamates, acylsarcosinates, acyl taurides, isethionates, soaps such as stearates, palmitates, resinates, oleates, linoleates and alkyl ether carboxylates. Anionic phosphate esters and alkyl phosphonates, alkylamino and imino methylene phosphonates may also be used.

[0256] In each case the anionic surfactant typically contains at least one alkyl or alkenyl chain having from 8 to 22 or from 10 to 20 carbon atoms. The expression “ether” here-in-before refers to compounds containing one or more glyceryl groups and / or oxyalkylene or polyoxyalkylene groups and especially a group containing from 1 to 150 oxyethylene and / or oxypropylene groups. One or more oxybutylene groups may additionally or alternatively be present. For example, the sulfonated or sulfated surfactant may be sodium dodecyl benzene sulfonate, potassium hexadecyl benzene sulfonate, sodium dodecyl, dimethyl benzene sulfonate, sodium lauryl sulfate, sodium tallow sulfate, potassium oleyl sulfate, ammonium lauryl sulfate, sodium tallow sulfate, potassium oleyl sulfate, ammonium lauryl monoethoxy sulfate, or monethanolamine cetyl 10 mole ethoxylate sulfate.

[0257] In some embodiments, the anionic surfactant is a sodium salt. Salts of commercial interest include those of potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine, alkyl amines containing up to seven aliphatic carbon atoms, and alkyl and / or hydroxyl alkyl phosphonium.

[0258] In some embodiments, the at least one further surfactant (C) comprises or consists of a mixture of two or more of the surfactants described hereinabove. The two or more surfactants may be of the same or different ionicity. In some embodiments, mixtures of non-ionic surfactants with cationic and / or amphoteric surfactants may be used. Typically, mixtures of anionic and cationic surfactants are avoided, which are often less mutually compatible.

[0259] According to the method of the present disclosure, when an effective amount of (A) and (B) are used, hydrate blockage is inhibited. In the absence of such effective amounts, hydrate blockage is not inhibited.

[0260] The disclosed method is particularly useful for treatment of lighter and / or low-boiling, Ci to Cs hydrocarbon gases or gas mixtures at elevated pressure and / or low temperature conditions. Non-limiting examples of such "low-boiling" gases include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and mixtures thereof as for example those encountered in natural gas including various natural gas mixtures that are present in many gas and / or oil formations and natural gas liquids (NGL). The hydrates of all these low-boiling hydrocarbons are also referred to as gas hydrates. In some embodiments, methods according to this disclosure are useful for inhibiting gas hydrate formation in a variety of black oils, heavy black oils to condensates, from API 10-60. The hydrocarbons and hydrocarbon gases may also comprise other compounds including, but not limited to hydrogen, carbon dioxide, hydrogen sulfide, and other compounds commonly found in gas / oil formations or processing plants, either naturally occurring or used in recovering / processing hydrocarbons from the formation or both, and mixtures thereof.

[0261] In some embodiments, the method disclosed herein is applied to fluids that contain various levels of oil, brine, or both having various levels of salinity. In at least one embodiment, the fluid has a salinity of about 0.8 to about 25 wt.-% or about 10 to about 25 wt.-%.

[0262] In some embodiments, the method disclosed herein is applied to a hydrocarbon system containing various levels of water cut. Here, "water cut" refers to the volume percent of water in a composition containing oil and water. In some embodiments, the water cut is from about 1 to about 90 vol.-%, from about 5 to about 90 vol.-%, from about 10 to about 90 vol.-%, from about 1 to about 85 vol.-%, from about 5 to about 85 vol.-%, from about 10 to about 85 vol.-%, from about 1 to about 80 vol.-%, from about 5 to about 80 vol.-%, from about 10 to about 80 vol.-%, from about 1 to about 75 vol.-%, from about 5 to about 75 vol.-%, from about 10 to about 75 vol.-%, from about 1 to about 70 vol.-%, from about 5 to 70 vol.-%, from about 10 to about 70 vol.-%, from about 1 to about 60 vol.-%, from about 5 to 60 vol.-%, from about 10 to about 60 vol.-%, from about 1 to about 50 vol.-%, from about 5 to 50 vol.-%, or from about 10 to about 50 vol.-%, with respect to the total volume of water and hydrocarbon phases. Accordingly, the synergistic combination of amphiphile (A) and surfactant (B), as described in various aspects of this disclosure, significantly expands the range of treatable water cuts compared to using either component individually. The amphiphile (A), the at least one surfactant (B), and, optionally, the at least one further surfactant (C) are contacted with the system of hydrocarbons and water at any concentration effective to inhibit the formation of hydrates under the given conditions. In some embodiments, the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.001 wt%, e.g., at least 0.005 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.01 wt%, e.g., at least 0.05 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.1 wt%, e.g., at least 0.2 or at least 0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.4 wt%, e.g., at least 0.5 or at least 0.6 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbons. In various embodiments, the combined concentration of (A), (B), and, if present, (C) in the mixture of hydrocarbons and water is at least 0.7 wt%, e.g., at least 0.8 or at least 0.9 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. For example, in various embodiments, the combined concentration of (A), (B), and, if present, (C) in the mixture of hydrocarbons and water is in the range of 0.001 wt%-8 wt%, e.g., in the range of 0.001 -2 wt%, or 0.001 -1 wt%, or 0.005-8 wt%, or 0.005-2 wt%, or 0.005- 1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the combined concentration of (A), (B), and, if present, (C) in the mixture of hydrocarbons and water is in the range of 0.01 wt%-8 wt%, e.g., in the range of 0.01 -2 wt%, or 0.01 -1 wt%, or 0.05-8 wt%, or 0.05-2 wt%, or 0.05-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the combined concentration of (A), (B), and, if present, (C) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-8 wt%, e.g., in the range of 0.1 -2 wt%, or 0.1 -1 wt%, or 0.2-8 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.3- 8 wt%, or 0.3-2 wt%, or 0.3-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the combined concentration of (A), (B), and, if present, (C) in the mixture of hydrocarbons and water is in the range of 0.4 wt%-8 wt%, e.g., in the range of 0.4- 2 wt%, or 0.4-1 wt%, or 0.5-8 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.6-8 wt%, or 0.6-2 wt%, or 0.6-1 .4 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the combined concentration of (A), (B), and, if present, (C) in the mixture of hydrocarbons and water is in the range of 0.7 wt%-8 wt%, e.g., in the range of 0.7- 2 wt%, or 0.7-1 .5 wt%, or 0.8-8 wt%, or 0.8-2 wt%, or 0.8-1 .6 wt%, or 0.9-8 wt%, or 0.9-2 wt%, or 0.9-17 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0263] In some embodiments, the concentration of (A) in the mixture of hydrocarbons and water is at least 0.001 wt%, e.g., at least 0.005 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is at least 0.01 wt%, e.g., at least 0.05 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is at least 0.1 wt%, e.g., at least 0.2 or at least 0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is at least 0.4 wt%, e.g., at least 0.5 or at least 0.6 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is at least 0.7 wt%, e.g., at least 0.8 or at least 0.9 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. For example, in various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.001 wt%-8 wt%, e.g., in the range of 0.001-2 wt%, or 0.001 -1 wt%, or 0.005-8 wt%, or 0.005-2 wt%, or 0.005-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.01 wt%-8 wt%, e.g., in the range of 0.01 -2 wt%, or 0.01 -1 wt%, or 0.05-8 wt%, or 0.05- 2 wt%, or 0.05-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-8 wt%, e.g., in the range of 0.1 -2 wt%, or 0.1 -1 wt%, or 0.2-8 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.3-8 wt%, or 0.3-2 wt%, or 0.3-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.4 wt%-8 wt%, e.g., in the range of 0.4- 2 wt%, or 0.4-1 wt%, or 0.5-8 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.6-8 wt%, or 0.6-2 wt%, or 0.6-1 .4 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.7 wt%-8 wt%, e.g., in the range of 0.7-2 wt%, or 0.7-1 .5 wt%, or 0.8-8 wt%, or 0.8-2 wt%, or 0.8-1 .6 wt%, or 0.9-8 wt%, or 0.9-2 wt%, or 0.9-17 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0264] In some embodiments, the concentration of (B) in the mixture of hydrocarbons and water is at least 0.001 wt%, e.g., at least 0.005 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is at least 0.01 wt%, e.g., at least 0.02 wt%, or at least 0.03 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is at least 0.04 wt%, e.g., at least 0.06 or at least 0.08 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is at least 0.1 wt%, e.g., at least 0.12 or at least 0.14 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is at least 0.16 wt%, e.g., at least 0.18 or at least 0.2 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. For example, in various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.001 wt%-2 wt%, e.g., in the range of 0.001 -0.5 wt%, or 0.001 -0.3 wt%, or 0.005-2 wt%, or 0.005-0.5 wt%, or 0.005-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.01 wt%-2 wt%, e.g., in the range of 0.01 -0.5 wt%, or 0.01 -0.3 wt%, or 0.02-2 wt%, or 0.02-0.5 wt%, or 0.02-0.3 wt%, or 0.03-2 wt%, or 0.03-0.5 wt%, or 0.03-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.04 wt%-2 wt%, e.g., in the range of 0.04-0.5 wt%, or 0.04-0.3 wt%, or 0.06-2 wt%, or 0.06-0.5 wt%, or 0.06-0.3 wt%, or 0.08-2 wt%, or 0.08-0.5 wt%, or 0.08-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-2 wt%, e.g., in the range of 0.1 -0.5 wt%, or 0.1 -0.3 wt%, or 0.12-2 wt%, or 0.12-0.5 wt%, or 0.12-0.3 wt%, or 0.14-2 wt%, or 0.14-0.5 wt%, or 0.14-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.16 wt%-2 wt%, e.g., in the range of 0.16-0.5 wt%, or 0.16-0.31 wt%, or 0.18-2 wt%, or 0.18-0.5 wt%, or 0.18-0.32 wt%, or 0.2-2 wt%, or 0.2-0.5 wt%, or 0.2-0.35 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0265] In some embodiments, the concentration of (C) in the mixture of hydrocarbons and water is at least 0.001 wt%, e.g., at least 0.005 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is at least 0.01 wt%, e.g., at least 0.05 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is at least 0.1 wt%, e.g., at least 0.2 or at least 0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is at least 0.4 wt%, e.g., at least 0.5 or at least 0.6 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is at least 0.7 wt%, e.g., at least 0.8 or at least 0.9 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. For example, in various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is in the range of 0.001 wt%-8 wt%, e.g., in the range of 0.001-2 wt%, or 0.001 -1 wt%, or 0.005-8 wt%, or 0.005-2 wt%, or 0.005-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is in the range of 0.01 wt%-8 wt%, e.g., in the range of 0.01 -2 wt%, or 0.01 -1 wt%, or 0.05-8 wt%, or 0.05- 2 wt%, or 0.05-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-8 wt%, e.g., in the range of 0.1 -2 wt%, or 0.1 -1 wt%, or 0.2-8 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.3-8 wt%, or 0.3-2 wt%, or 0.3-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is in the range of 0.4 wt%-8 wt%, e.g., in the range of 0.4- 2 wt%, 0.4-1.5 wt%, or 0.4-1 wt%, or 0.5-8 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.6-8 wt%, or 0.6-2 wt%, or 0.6-1 .4 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. In various embodiments, the concentration of (C) in the mixture of hydrocarbons and water is in the range of 0.7 wt%-8 wt%, e.g., in the range of 0.7-2 wt%, or 0.7-1.5 wt%, or 0.8-8 wt%, or 0.8-2 wt%, or 0.8-1 .6 wt%, or 0.9-8 wt%, or 0.9-2 wt%, or 0.9-17 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0266] As compared to the total dose rate of either (A) or (B) individually, the total dose rate of (A) + (B) needed to prevent hydrate agglomeration may in various embodiments be reduced by from 10 to 70 wt.-%, from 10 to 60 wt.-%, from 10 to 50 wt.-%, from 10 to 40 wt.-%, 20 to 70 wt.-%, from 20 to 60 wt.-%, from 20 to 50 wt.-%, from 20 to 40 wt.-%, from 30 to 70 wt.-%, from 30 to 60 wt.-%, from 30 to 50 wt.-%, from 30 to 40 wt.-%, from 40 to 70 wt.-%, from 40 to 60 wt.-%, from 40 to 50 wt.-%, from 50 to 70 wt.-%, or from 50 to 60 wt.-%. Prevention of hydrate agglomeration can be further reduced in the presence of optional component (C). As compared to the total dose rate of (A), (B), or (C) individually, the total dose rate of (A) + (B) + (C) needed to prevent hydrate agglomeration may in various embodiments be reduced by from 10 to 70 wt.-%, from 10 to 60 wt.-%, from 10 to 50 wt.-%, from 10 to 40 wt.-%, 20 to

[0267] 70 wt.-%, from 20 to 60 wt.-%, from 20 to 50 wt.-%, from 20 to 40 wt.-%, from 30 to

[0268] 70 wt.-%, from 30 to 60 wt.-%, from 30 to 50 wt.-%, from 30 to 40 wt.-%, from 40 to

[0269] 70 wt.-%, from 40 to 60 wt.-%, from 40 to 50 wt.-%, from 50 to 70 wt.-%, or from 50 to 60 wt.-%.

[0270] The contacting of amphiphile (A), the at least one surfactant (B), and, optionally, at least one further surfactant (C) to the mixture of hydrocarbons and water may be achieved in a number of ways, including mixing, blending with mechanical mixing equipment or devices, stationary mixing setup or equipment, magnetic mixing or other suitable methods, other equipment and means known to one skilled in the art and combinations thereof to provide adequate contact and / or dispersion of (A), (B), and, optionally, (C) in the mixture. The contacting can be made in-line or batchwise or both. The components (A), (B), and, optionally, (C) may be mixed prior to or during contact, or both. If needed or desired, the components (A), (B), and, optionally, (C) may be optionally removed or separated mechanically, chemically, or by other methods known to one skilled in the art, or by a combination of these methods after the hydrate formation conditions are no longer present.

[0271] Contacting of the amphiphile (A), the at least one surfactant (B), and, optionally, at least one further surfactant (C) to hydrocarbons and water can be conducted prior to substantial formation of hydrates or even prior to the onset of hydrate formation. This may be at high temperatures such as, for instance, temperatures prevailing downhole, at low pressures, and / or at low water-cuts. The amphiphile (A), the at least one surfactant (B), and optionally, at least one further surfactant (C) may be introduced into the fluid comprising gas and water through a conduit or an injection point. In certain embodiments, the amphiphile (A), the at least one surfactant (B), and optionally, at least one further surfactant (C) may be introduced into a wellbore, a conduit, a vessel, and the like and may contact and / or be introduced into a fluid residing therein. An exemplary application point for the petroleum liquid production operations is to introduce hydrate inhibitor into the subsea wellhead itself, upstream of the well choke valve. This ensures that during a shut-in the composition can disperse throughout the area where natural gas hydrates have the highest risk of occurring. Application of the amphiphile (A), the at least one surfactant (B), optionally, at least one further surfactant (C) can also occur at other areas in the wellhead or flowline manifold or the flowline itself, considering the density of the injected liquid. If the injection point is well above the gas hydrate formation depth, then the amphiphile (A), the at least one surfactant (B), and optionally, at least one further surfactant (C) may be formulated with a solvent having a density high enough that (A), (B), and (C) will sink in the flowline to collect at the water / oil interface. In some embodiments, application is also used in pipelines or anywhere in the system where the potential for agglomerates of gas hydrate formation exists.

[0272] The method disclosed herein is equally applicable for fluids that are flowing and those that are substantially stationary. Accordingly, the fluid may be within a vessel, or within a conduit (e.g., a conduit that may transport the fluid), or within a subterranean formation and / or a wellbore penetrating a portion of the subterranean formation. Examples of conduits include, but are not limited to, pipelines, production piping, subsea tubulars, process equipment, and the like as used in industrial settings and / or as used in the production of oil and / or gas from a subterranean formation, and the like. The conduit may in certain embodiments penetrate at least a portion of a subterranean formation, as in the case of an oil and / or gas well. In particular embodiments, the conduit may be a wellbore or may be located within a wellbore penetrating at least a portion of a subterranean formation. Such oil and / or gas well may, for example, be a subsea well (e.g., with the subterranean formation being located below the sea floor), or it may be a surface well (e.g., with the subterranean formation being located belowground). A vessel or conduit according to other embodiments may be located in an industrial setting such as a refinery (e.g., separation vessels, dehydration units, pipelines, heat exchangers, and the like), or it may be a transportation pipeline.

[0273] The method disclosed herein is particularly suitable for lower boiling hydrocarbons or hydrocarbon gases at ambient temperature when the pressure is at or greater than atmospheric pressure ( / .e. about 101 kPa), greater than about 6 MPa, greater than about 30 MPa, or even up to about 100 MPa. There is no specific high-pressure limit. The present method can be used at any pressure that allows formation of hydrocarbon gas hydrates. Lower temperatures tend to favor hydrate formation, thus requiring the treatment according to the method of the present disclosure; at much higher temperatures, however, hydrocarbon hydrates are less likely to form, thus obviating the need of carrying out any treatments.

[0274] The method disclosed herein may be used in combination with other means of hydrate inhibition, such as the use of thermodynamic or kinetic inhibitors discussed hereinabove. These other hydrate inhibitors may be of the same or different type of hydrate inhibitor as (A), (B), and (C). If mixtures of hydrate inhibitors are used, the mixture may be added to the hydrocarbon and water containing process stream through a single port or multiple ports. Alternatively, individual hydrate inhibitors may be added at separate ports to the process stream.

[0275] The method disclosed herein may also be used in combination with other oil field flow assurance and integrity compounds such as, but not limited to, corrosion inhibitors, scale inhibitors, paraffin inhibitors, asphaltene inhibitors, drilling fluids, fracturing fluids, completion fluids, antifoams, emulsion breakers, and / or water clarifiers.

[0276] The present disclosure further provides a hydrate inhibitor composition comprising, an amphiphile (A) and at least one surfactant (B), wherein the amphiphile (A) and the at least one surfactant (B) are as defined hereinabove. The composition can also include at least one further surfactant (C), as defined hereinabove. The composition disclosed herein contains (A), (B), and, optionally, (C) in the weight ratios and / or the weight percentages described hereinabove. The present disclosure further provides a formulation comprising (A), (B), and, optionally, (C), wherein (A), (B), and (C) are as defined above. The formulation disclosed herein contains (A), (B), and, optionally, (C) in the weight ratios and / or the weight percentages described hereinabove.

[0277] In some embodiments, the formulation disclosed herein further comprises one or more diluents. Preferred diluents are generally solvents for the virgin form of the active ingredients. Such solvents include, but are not limited to monohydric alcohols having 1 to 12 carbon atoms like methanol, ethanol, n-propanol, iso-propanol, n- butanol, iso-butanol, tert-butanol, pentanol, hexanol, heptanol, octan-1 -ol, octan-2- ol and 2-ethylhexan-1 -ol; glycols like ethylene glycol, 1 ,2-propylene glycols, 1 ,3-propylene glycol, hexylene glycol and glycerol; ether solvents like ethylene glycol mono butylether (butyl cellosolve), ethylene glycol dibutyl ether, and tetrahydrofuran; ketonic solvents like acetone, methylethylketone, diisobutylketone, N-methylpyrrolidone, cyclohexanone; acetonitrile; esters such as ethyl acetate, propyl acetate and butyl acetate; and mixtures thereof. In a further preferred embodiment, a higher boiling aliphatic, aromatic or alkylaromatic hydrocarbon, or a mixture thereof has proven to be advantageous. Most preferred solvents are methanol, ethanol, glycerol, decane, toluene, xylene, diethylbenzene, naphthalene, tetralin, decalin, and commercial solvent mixtures such as Shellsol®, Exxsol®, Isopar®, Solvesso® types, diesel, Solvent Naphtha and / or kerosene. The more polar organic solvents like for example monohydric and polyhydric alcohols having 1 to 5 and especially having 1 to 3 carbon atoms may also be used in admixture with water, brine, and / or seawater. The selection of a suitable diluent or combination of diluents is important to maintain a stable solution of the compounds during storage and to provide stability and reduced viscosity for the inhibitor solutions when they are injected against a pressure of about 1 .3 MPa to about 200 MPa.

[0278] If a diluent is present in the formulation, its concentration is in the range of from about 1 to about 95 wt.-%, from about 1 to about 90 wt.-%, from about 1 to about 80 wt.-%, from about 10 to about 95 wt.-%, from about 10 to about 90 wt.-%, from about 10 to about 80 wt.-%, from about 20 to about 95 wt.-%, from about 20 to about 90 wt.-%, or from about 20 to about 80 %, based on the weight of the formulation comprising (A), (B), optionally (C), and the diluent. Such formulations can be delivered through subsea umbilicals.

[0279] In some embodiments, finished product formulations are made to approximately from 40 to 75 wt.-%, such as 60 wt.-%, active content and from 25 to 60 wt.-%, such as 40 wt.-%, of a solvent. They are made as active as possible to save on space, logistics, and pump capacity which are all relevant concerns when treating production fluids offshore. However, often the maximum viscosity specified for a concrete application (commonly <100 mPa.s at 4°C) sets an upper limit.

[0280] Examples

[0281] Test Procedure 1: Evaluation of hydrate inhibitor formulations.

[0282] Hydrate inhibition performance was assessed in rocking cells, which are widely used to assess anti-agglomerant performance. They are designed to simulate conditions in oil and gas pipelines where hydrates might form. Rocking cells are typically made with sapphire windows, allowing for visual observation of the contents during the experiment. Each cell has a total volume of about 20 mL, with tests usually using 10 mL of liquid (50% liquid load), and can be pressurized (up to 5000 psi, 345 bar, 34.5 MPa) to simulate pipeline conditions. The cells are housed in a temperature- controlled bath, allowing for precise temperature regulation. The rocking motion simulates the flow of fluids in a pipeline, ensuring good mixing of the contents. A 12 mm ball bearing is placed inside the cell and as the cells rock, the ball bearing rolls back and forth, providing additional mixing and allowing assessment of the viscosity and physical properties of the system. Sensors at either end of the cell detect the movement of the ball bearing, providing data on its travel time from one end of the cell to the other.

[0283] In conducting the tests, the cells were filled with a mixture of oil, water (brine), gas, and the hydrate inhibitor being tested (or no hydrate inhibitor in the case of a blank). They were then subjected to a series of temperature and pressure changes while rocking, simulating real-world pipeline conditions. Hydrate formation was visually observed through the sapphire windows and the movement of the ball bearings could indicate the formation of hydrate particles or plugs. A test is generally considered to be a pass if no hydrate particles or plugs are visually observed, and the ball bearing moves freely throughout the test duration. A test is generally considered to be a fail if hydrate deposits form or if the ball bearing's movement is significantly impeded.

[0284] Rocking cells are particularly useful for testing anti-agglomerants at water cuts ranging from 10-50%, though they can be used outside this range. They provide a way to visually observe hydrate formation and dispersion, making them valuable tools in hydrate inhibitor research and development.

[0285] Example 1: Comparative Performance in Dodecane

[0286] Comparative performance testing was performed in dodecane with a water cut of 50%. The brine composition was 5 wt.-% NaCI and the gas composition was as shown in Table 1 .

[0287] Table 1 : Gas Composition

[0288] Based on the brine and gas composition, hydrate equilibrium curves were generated using Multiflash modeling. On this basis, the pressure and temperature of the experiment could be used to determine the sub-cooling of the system. Herein, “subcooling” refers to the temperature difference between the system test conditions (in this case 40°F) and the temperature at which hydrates are predicted to form without treatment at the system pressure (71.41 °F, 21.89°C), i.e. a difference of 31.41 °F (17.49°C). The system conditions are summarized below.

[0289] Pressure: 2000 psi (13.79

[0290] MPa) Temperature: 40°F (4.4°C)

[0291] Sub-cooling: 31 .41 °F (17.45°C)

[0292] The amphiphiles (A) and surfactants (B) used in these experiments are indicated in Tables 2 and 3, respectively. Table 2: Characterization of Tested Amphiphiles (A) In the amphiphiles A1 to A4, q is 1 . “Coconut cut fatty acyl” comprises as main components 51 wt.-% C12 fatty acyl and 16 wt.-% C14 fatty acyl.” Table 3: Characterization of Tested Surfactants (B)

[0293] The MED of each amphiphile (A) and surfactant (B), individually, was determined according to Test Procedure 1. Performance testing was started with 0.7 wt.-% by volume water of the amphiphile (A) or surfactant (B), formulated as a 60 % active solution in methanol. Samples that failed at this dose rate were labelled as >0.7 wt.- % minimum effective dose (MED) and were not tested further. Samples that passed at 0.7 wt.-% were sequentially and incrementally treated with reduced dosage in steps of 0.1 wt.-% until a failure was observed. The lowest passing dose rate was determined to be the Minimum Effective Dose (MED). The values listed for MED in Table 4 refer to the required minimum dosage of active ingredient in relation to the volume of brine in the system.

[0294] Table 4: Results from Rocking Cell Testing ((A) or (B), individually, in dodecane)

[0295] Gas hydrate inhibitor sample formulations were prepared by blending the amphiphiles (A) of Table 2 and the surfactants (B) of Table 3 in the weight ratios according to Table 5. For ease of handling, the formulations were adjusted to 60 wt.-% active content with methanol. In this case, performance testing was started with 0.5 wt.-% by volume water of the amphiphile (A) or surfactant (B), formulated as a 60 % active solution in methanol. Samples that failed at this dose rate were labelled as >0.5 wt.-% minimum effective dose (MED) and were not tested further. Samples which passed at 0.5% are either labelled with an MED <0.5% or were further tested at 0.3%. The MED of each sample formulation is presented in Table 5.

[0296] Table 5: Results from Rocking Cell Testing (formulations containing (A) + (B) in dodecane)

[0297] As shown by the data above, the combination of amphiphile (A2) and surfactant (B1 ) or (B2) results in a lower minimum effect dose than that achieved by the individual components alone. Accordingly, these data demonstrate a synergistic effect between (A) and (B). Example 2: Comparative Performance B in Oil

[0298] Comparative performance testing was performed in an oil collected from the Gulf of Mexico region and which flows with a field water cut in the range of 2-10%. The salinity of produced water was measured to be between 40,000 and 50,000 ppm TDS (Total Dissolved Solids).

[0299] Table 6 shows the specific brine composition that was used in the rocking cell test to mimic the field conditions. The gas composition was the same as shown in Table 1 hereinabove.

[0300] Table 6: Brine Composition

[0301] As described for Example 1 , the sub-cooling at the system pressure and temperature was determined by modeling the hydrate curve in Multiflash. The system conditions are shown below:

[0302] Pressure: 2900 psi (20 MPa)

[0303] Temperature: 39.48°F (4.16°C)

[0304] Sub-cooling: 31 ,98°F (17.77°C) The amphiphiles (A) and surfactants (B) used in these experiments were the same as in Example 1. The MED of each amphiphile (A) and surfactant (B), individually, was determined according to Test Procedure 1. Performance testing was started with 2.0 wt.-% by volume water of the amphiphile (A) or surfactant (B), formulated as a 60 % active solution in methanol. Samples that failed at this dose rate were labelled as >2.0 wt.-% minimum effective dose (MED) and were not tested further. Samples that passed at 2.0 wt.-% were sequentially and incrementally treated with reduced dosage in steps of 0.1 wt.-% until a failure was observed. The lowest passing dose rate was determined to be the Minimum Effective Dose (MED).

[0305] The values listed for MED in Table 7 refer to the required minimum dosage of active ingredient in relation to the volume of brine in the system.

[0306] Table 7: Results from Rocking Cell Testing: (A) or (B), individually

[0307] Gas hydrate inhibitor sample formulations were prepared by blending the amphiphiles (A) of Table 2 and the surfactants (B) of Table 3 in the weight ratios according to Table 8. For ease of handling, the formulations were adjusted to 60 wt.-% active content with methanol. Rocking cell testing was performed as described for Example 1 and the MED was likewise determined.

[0308] The MED of each sample formulation is presented in Table 8. Table 8: Results from Rocking Cell Testing: formulations containing (A) + (B) in oil

[0309] As shown by the data above, the combination of amphiphile (A2) and surfactant (B1 )-(B5) results in a lower minimum effect dose than that achieved by the individual components alone. Accordingly, these data demonstrate a synergistic effect between (A) and (B).

[0310] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.

[0311] In the embodiments below, the term “any non-inconsistent previous embodiment” and similar terms have a broad meaning. Accordingly, if an earlier embodiment recites only that X is in the range of 1-5, and a later embodiment depends from “any non-inconsistent embodiment above” and recites that X is 1 -10, it is specifically contemplated that in the later embodiment X can alternatively be 1 -5. Moreover, the various embodiments below can be combined in any number and in any combination that is not technically or logically inconsistent to provide other specifically contemplated embodiments.

[0312] Embodiment 1. A method for inhibiting the formation of gas hydrate agglomerates and / or plugs, the method comprising bringing a system containing hydrocarbons and water into contact with at least one amphiphile (A) each of the formula (1a) or (1 b) R5-L-N(R1)(R2) (1 a)

[0313] [R5— L— N(R1)(R2)(R3)]q+[X-]q(1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or R1and R2, together with the nitrogen to which they are attached, form a heterocycle;

[0314] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;

[0315] L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from nitrogen and oxygen, and optionally one or more further heteroatoms;

[0316] R5is a hydrocarbyl group having from 6 to 24 carbon atoms;

[0317] X’ is an anion; and q is 0 or an integer from 1 to 7; and at least one surfactant (B) each comprising an imidazoline head group and a C9-C19 linear hydrocarbyl tail, wherein the at least one amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio of from 95:5 to 5:95.

[0318] Embodiment 2. The method according to embodiment 1 , wherein the at least one amphiphile (A) includes (or is) an amphiphile of formula (1 a). Embodiment 3. The method according to any non-inconsistent previous embodiment, wherein the at least one amphiphile (A) includes (or is) an amphiphile of the formula (1 b).

[0319] Embodiment 4. The method according to embodiment 3, wherein in one or more amphiphiles (e.g., each amphiphile) of the formula (1 b) the linking moiety L does not carry any cationic charge, and q is 1 .

[0320] Embodiment 5. The method according to embodiment 3, wherein in one or more amphiphiles (e.g., each amphiphile) of the formula 1 (b) the linking moiety L carries one or more cationic charges, and q is an integer between 2 and 7.

[0321] Embodiment 6. The method according to any non-inconsistent previous embodiment, wherein each of R1and R2is, independently, an alkyl group having 3, 4, or 5 carbon atoms.

[0322] Embodiment 7. The method according to any non-inconsistent previous embodiment, wherein R1and R2each contain 4 carbon atoms.

[0323] Embodiment 8. The method according to any non-inconsistent previous embodiment, wherein R1and R2are independently selected from methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso-pentyl.

[0324] Embodiment 9. The method according to any non-inconsistent previous embodiment, wherein R1and R2are independently selected from n-butyl, iso-butyl, and tert-butyl.

[0325] Embodiment 10. The method according to any non-inconsistent previous embodiment, wherein R1and R2are both n-butyl.

[0326] Embodiment 11. The method according to any non-inconsistent previous embodiment, wherein R1and R2, together with the nitrogen to which they are attached, form a nitrogen-containing heterocycle that is optionally substituted, fully saturated or unsaturated, and aromatic or nonaromatic.

[0327] Embodiment 12. The method according to any non-inconsistent previous embodiment, wherein R1and R2, together with the nitrogen to which they are attached, form a nitrogen-containing heterocycle that is selected from pyrrole, pyrroline, pyrrolidine, piperidine, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, triazole, isoxazole, isoxazoline, isoxazolidine, oxazole, oxazoline, oxazolidine, thiazole, isothiazole, oxadiazole, oxatriazole, dioxazole, oxathiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, oxazine, oxathiazine, oxazine, isoxazine, oxadiazine, morpholine, azepane, azepine, caprolactam, and quinoline.

[0328] Embodiment 13. The method according to any non-inconsistent previous embodiment, wherein R1and R2, together with the nitrogen to which they are attached, form a nitrogen-containing heterocycle that is substituted with one or more of a Ci-C20alkyl, a C2-C20alkenyl, an aryl, an aralkyl, a hydroxyl, an acyl, an acyloxy, an alkoxy, an alkenoxy, an aryloxy, a halogen, an amino, a nitro, a cyano, an ester, and an ether.

[0329] Embodiment 14. The method according to any non-inconsistent previous embodiment, wherein R3is hydrogen.

[0330] Embodiment 15. The method according to any non-inconsistent previous embodiment, wherein R3is an alkyl group having from 1 to 5 or from 1 to 4 carbon atoms.

[0331] Embodiment 16. The method according to any non-inconsistent previous embodiment, wherein R3is a methyl or an ethyl group.

[0332] Embodiment 17. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain that is made up of from 3 to 160, from 20 to 140, from 40 to 120, or from 60 to 100 linking elements.

[0333] Embodiment 18. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain that is made up of from 4 to 20, from 5 to 20, from 6 to 20, from 4 to 14, from 5 to 14, from 6 to 14, from 4 to 12, from 5 to 12, from 6 to 12, from 4 to 10, from 5 to 10, or from 6 to 10 linking elements.

[0334] Embodiment 19. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain comprising one or more aliphatic groups having from 2 to 10, from 3 to 6, or from 2 to 4 adjacent carbon atoms.

[0335] Embodiment 20. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain comprising an aliphatic group selected from ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0336] Embodiment 21. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain comprising from 2 to 4 adjacent carbon atoms.

[0337] Embodiment 22. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain comprising a saturated or unsaturated heteroaliphatic chain comprising a linear or branched chain of carbon atoms that is interrupted by at least one heteroatom.

[0338] Embodiment 23. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain wherein at least some of the carbon atoms in the connecting chain are connected to each other and / or to the hydrophobic tail by a heteroatom. Embodiment 24. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain wherein one or more hydrocarbyl segments each having from 2 to 10, from 3 to 6, or from 2 to 4 adjacent carbon atoms are connected to each other and / or to the hydrophobic tail by a heteroatom.

[0339] Embodiment 25. The method according to any non-inconsistent previous embodiment, wherein the heteroatom is nitrogen and oxygen.

[0340] Embodiment 26. The method according to any non-inconsistent previous embodiment, wherein not more than one heteroatom is connected to an individual carbon atom.

[0341] Embodiment 27. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain comprising a heteroaliphatic chain made up of at least 2 adjacent carbon atoms and at least one heteroatom selected from oxygen and nitrogen.

[0342] Embodiment 28. The method according to any non-inconsistent previous embodiment, wherein connecting chain comprises one or more additional heteroatoms are selected from nitrogen, oxygen, phosphorous, and sulfur.

[0343] Embodiment 29. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain that is part of a functional group.

[0344] Embodiment 30. The method according to any non-inconsistent previous embodiment, wherein the functional group is selected from C(=O)O, O-C(=O), C(=O)N(R6), C(=O)N(R6), N(R7)C(=O), N(R7)C(=O), -N(R6)-, -(R7)N-, -O-, -S-, -(SO)- or -(SO2)-, wherein R6is hydrogen or an alkyl group having from 1 to 5 carbon atoms or from 3 to 5 carbon atoms and R7is hydrogen or an organic moiety having from 1 to 20 carbon atoms. Embodiment 31. The method according to any non-inconsistent previous embodiment, wherein R6is hydrogen or an alkyl group having from 1 to 4 carbon atoms.

[0345] Embodiment 32. The method according to any non-inconsistent previous embodiment, wherein the connecting chain includes at least one carbon atom that is part of a carbonyl or a carboxymethyl group.

[0346] Embodiment 33. The method according to any non-inconsistent previous embodiment, wherein the connecting chain includes at least one nitrogen atom that is part of an amino, a polyamino, an ammonium, a polyammonium, an amide, or an imide group.

[0347] Embodiment 34. The method according to any non-inconsistent previous embodiment, wherein the connecting chain includes at least one nitrogen atom that is in the form of an amine or amide group.

[0348] Embodiment 35. The method according to any non-inconsistent previous embodiment, wherein the connecting chain includes one or more heteroatoms that are part of a functional group selected from an ester, an amide, and an imide group.

[0349] Embodiment 36. The method according to any non-inconsistent previous embodiment, wherein the carbon atom of the carbonyl group and the nitrogen or oxygen of the functional group are included as linking elements in the connecting chain.

[0350] Embodiment 37. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain wherein one or more atoms in the connecting chain are substituted with one or more heteroatoms. Embodiment 38. The method according to any non-inconsistent previous embodiment, wherein the one or more heteroatoms are part of a hydroxyl group, an amino group, a carboxylic acid group, or a carboxylate group.

[0351] Embodiment 39. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L comprises a connecting chain wherein one or more atoms in the connecting chain are substituted with an alkyl group.

[0352] Embodiment 40. The method according to any non-inconsistent previous embodiment, wherein the alkyl group contains from 1 to 6 carbon atoms.

[0353] Embodiment 41. The method according to any non-inconsistent previous embodiment, wherein the linking moiety L is selected from the chemical structures (2) to (12):

[0354] -C(=O)-N(R6)-(CH2)t- (2)

[0355] -N(R7)-C(=O)-(CH2)t- (3)

[0356] -N(R7)-(CH2)2-C(=O)-NH-(CH2)t- (4)

[0357] -N(R7)-C(=O)-(CH2)2-N(R6)-(CH2)t- (5)

[0358] -CH(OH)-CH2-N(R6)-(CH2)t- (6)

[0359] -CH(COOH)-CH2-C(=O)-N(R6)-(CH2)t- (7a)

[0360] -CH(CH2-COOH)-C(=O)-N(R6)-(CH2)t- (7b)

[0361] -CH(COOH)-CH2-C(=O)-[O-(CH2)t]v- (8a)

[0362] -CH(CH2-COOH)-C(=O)-[O-(CH2)t]v- (8b)

[0363] -N(R7)-C(=O)-(CH2)2-C(=O)-N(R6)-(CH2)t- (9)

[0364] -N(R7)-C(=O)-CH2-CH(OH)-C(=O)-N(R6)-(CH2)t- (10a) -N(R7)-C(=O)-CH(OH)-CH2-C(=O)-N(R6)-(CH2)t- (10b)

[0365] -N(R7)-C(=O)-CH(OH)-CH(OH)-C(=O)-N(R6)-(CH2)t- (11 )

[0366] -N(R7)-C(=O)-C(OH)(CH2COOH)-CH2-C(=O)-N(R6)-(CH2)t- (12a)

[0367] -N(R7)-C(=O)-CH2-C(OH)(CH2COOH)-C(=O)-N(R6)-(CH2)t- (12b)

[0368] Embodiment 42. The method according to any non-inconsistent previous embodiment, wherein R6is an alkyl group having from 2 to 4 carbon atoms.

[0369] Embodiment 43. The method according to any non-inconsistent previous embodiment, wherein R7is an alkyl group having from 1 to 20 carbon atoms.

[0370] Embodiment 44. The method according to any non-inconsistent previous embodiment, wherein v is an integer from 1 to 10.

[0371] Embodiment 45. The method according to any non-inconsistent previous embodiment, wherein the amino groups are in the form of an ammonium compound.

[0372] Embodiment 46. The method according to any non-inconsistent previous embodiment, wherein R5is a hydrocarbyl group having from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms.

[0373] Embodiment 47. The method according to any non-inconsistent previous embodiment, wherein R5has a distribution such that at least 80 wt% of the R5groups are linear alkyl or alkenyl 8-14 carbons in length.

[0374] Embodiment 48. The method according to any non-inconsistent previous embodiment, wherein R5has a distribution such that at least 60 wt% of the R5groups are linear alkyl or alkenyl 10-14 (e.g., 11-13) carbons in length.

[0375] Embodiment 49. The method according to any non-inconsistent previous embodiment, wherein R5is a linear, branched, or cyclic alkyl or alkenyl group. Embodiment 50. The method according to any non-inconsistent previous embodiment, wherein R5is a linear, alkyl or alkenyl group.

[0376] Embodiment 51. The method according to any non-inconsistent previous embodiment, wherein R5is selected from hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, docosyl, tricosyl, tetracosyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, octadecadienyl, and eicosenyl.

[0377] Embodiment 52. The method according to any non-inconsistent previous embodiment, wherein R5is a mixture of hexadecenyl, octadecenyl, and eicosenyl.

[0378] Embodiment 53. The method according to any non-inconsistent previous embodiment, wherein X” is at least one anion selected from hydroxide, carboxylate, halide, sulfate, nitrite, nitrate, organic sulfonate, organic sulfate, phosphate, and organic phosphonate.

[0379] Embodiment 54. The method according to any non-inconsistent previous embodiment, wherein X” is carboxylic acid having from 1 to 20, from 2 to 20, from 3 to 20, from 1 to 12, from 2 to 12, from 3 to 12, from 1 to 6, from 2 to 6, or from 3 to 6 carbon atoms, wherein the carboxylic acid is linear or branched and is saturated or unsaturated.

[0380] Embodiment 55. The method according to any non-inconsistent previous embodiment, wherein X” is selected from acetate, halide, acrylate, and methacrylate.

[0381] Embodiment 56. The method according to any non-inconsistent previous embodiment, wherein X” is acrylate.

[0382] Embodiment 57. The method according to any non-inconsistent previous embodiment, wherein the anion is methylsulfate or ethylsulfate. Embodiment 58. The method according to any non-inconsistent previous embodiment, wherein q is an integer from 1 to 7 or an integer from 2 to 7.

[0383] Embodiment 59. The method according to any non-inconsistent previous embodiment, wherein q is 1 or 2, e.g., 1.

[0384] Embodiment 60. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) is of the general formula (13) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or the nitrogen atom and the R1and R2groups together form a substituted or unsubstituted heterocyclic group;

[0385] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2 position;

[0386] R4is selected from the group consisting of -(CH2)t-, -[(CH2-CHR1°)s]-, -(CH2- CHR10O)u-(CH2)t-, wherein s is 1 , 2, or 3, t is 2, 3, or 4, and u is an integer from 1 to 100;

[0387] R6is hydrogen or an alkyl group having from 1 to 5 or from 1 to 4 carbon atoms;

[0388] R7is hydrogen or an organic moiety having from 1 to 20 carbon atoms;

[0389] R8is hydrogen or an alkyl group having from 1 to 5 carbon atoms;

[0390] R9is hydrogen or an alkyl group having from 1 to 5 or from 1 to 4 carbon atoms;

[0391] R1° is an alkyl group having from 1 to 4 carbon atoms; m is 0 or 2, n is 0 or 1 , o is 0 or 2, p is 0 or an integer from 1 to 5; and q is an integer from 1 to 7, provided that q is not more than the sum of n + p +1 . Embodiment 61. The method according to any non-inconsistent previous embodiment, wherein R4is -(CH2-CHR10O)u-(CH2)t- and R10is an alkyl group having from 1 to 4 carbon atoms.

[0392] Embodiment 62. The method according to any non-inconsistent previous embodiment, wherein u is an integer from 1 to 25, from 1 to 10, or from 1 to 5.

[0393] Embodiment 63. The method according to any non-inconsistent previous embodiment, wherein R6is a methyl or a butyl group.

[0394] Embodiment 64. The method according to any non-inconsistent previous embodiment, wherein R9is a methyl or a butyl group.

[0395] Embodiment 65. The method according to any non-inconsistent previous embodiment, wherein R7is an alkyl group having from 1 to 20 carbon atoms.

[0396] Embodiment 66. The method according to any non-inconsistent previous embodiment, wherein R8is a methyl or a butyl group.

[0397] Embodiment 67. The method according to any non-inconsistent previous embodiment, wherein m is 0.

[0398] Embodiment 68. The method according to any non-inconsistent previous embodiment, wherein m is 2.

[0399] Embodiment 69. The method according to any non-inconsistent previous embodiment, wherein o is 0.

[0400] Embodiment 70. The method according to any non-inconsistent previous embodiment, wherein o is 2.

[0401] Embodiment 71. The method according to any non-inconsistent previous embodiment, wherein the sum of m + o is 2. Embodiment 72. The method according to any non-inconsistent previous embodiment, wherein n is 0.

[0402] Embodiment 73. The method according to any non-inconsistent previous embodiment, wherein n is 1.

[0403] Embodiment 74. The method according to any non-inconsistent previous embodiment, wherein p is 0.

[0404] Embodiment 75. The method according to any non-inconsistent previous embodiment, wherein p is an integer from 1 to 5.

[0405] Embodiment 76. The method according to any non-inconsistent previous embodiment, wherein n+p is an integer from 1 to 6.

[0406] Embodiment 77. The method according to any non-inconsistent previous embodiment, wherein n+p is 1.

[0407] Embodiment 78. The method according to any non-inconsistent previous embodiment, wherein q is an integer from 1 to 7.

[0408] Embodiment 79. The method according to any non-inconsistent previous embodiment, wherein q is an integer from 2 to 7.

[0409] Embodiment 80. The method according to any non-inconsistent previous embodiment, wherein m, n, and p are all 0.

[0410] Embodiment 81. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) is of the general formula (14) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or the nitrogen atom and the R1and R2groups together form a substituted or unsubstituted heterocyclic group;

[0411] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2 position;

[0412] R4is selected from -(CH2)t- and -[(CH2-CHR10)s]-;

[0413] R5is a hydrocarbyl group having from 6 to 24 carbon atoms;

[0414] R6is hydrogen or an alkyl group having from 1 to 5 carbon atoms;

[0415] R1° is an alkyl group having from 1 to 4 carbon atoms; p is an integer from 1 to 5; s is 1 , 2, or 3; t is 2, 3, or 4; q is 0 or 1 ; and

[0416] X” is an anion.

[0417] Embodiment 82. The method according to any non-inconsistent previous embodiment, wherein p is 1 or 2 or p is 1 .

[0418] Embodiment 83. The method according to any non-inconsistent previous embodiment, wherein R4is -(CH2)t- and t is 3.

[0419] Embodiment 84. The method according to any non-inconsistent previous embodiment, wherein R6is hydrogen.

[0420] Embodiment 85. The method according to any non-inconsistent previous embodiment, wherein R3is hydrogen and the anion X is selected from hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate. Embodiment 86. The method according to any non-inconsistent previous embodiment, wherein X” is acrylate.

[0421] Embodiment 87. The method according to any non-inconsistent previous embodiment, wherein

[0422] R1and R2are each independently selected from methyl, ethyl, n propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso pentyl;

[0423] R3is present as hydrogen or as an alkyl group having from 1 to 5 carbon atoms;

[0424] R4is -(CH2)t-;

[0425] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0426] R6is present as hydrogen; p is 1 or 2; t is 2, 3, or 4; q is 1 ; and

[0427] X” is selected from hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0428] Embodiment 88. The method according to any non-inconsistent previous embodiment, wherein

[0429] R1and R2are each independently selected from n propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso pentyl;

[0430] R3is present as hydrogen;

[0431] R4is -(CH2)t-;

[0432] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0433] R6is present as hydrogen; p is 1 ; t is 3; q is 1 ; and

[0434] X” is selected from hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0435] Embodiment 89. The method according to any non-inconsistent previous embodiment, wherein

[0436] R1and R2are each n-butyl;

[0437] R3is present as hydrogen;

[0438] R4is -(CH2)t-;

[0439] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0440] R6is present as hydrogen; p is 1 ; t is 3; q is 1 ; and

[0441] X” is selected from hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0442] Embodiment 90. The method according to any non-inconsistent previous embodiment, wherein

[0443] R1and R2are each independently selected from n-butyl, iso-butyl, tert-butyl, n-pentyl, and iso pentyl;

[0444] R3is present as an alkyl group having from 1 to 5 carbon atoms;

[0445] R4is -(CH2)t-;

[0446] R5is an alkyl or alkenyl group having from 6 to 24 carbon atoms, from 6 to 18 carbon atoms, from 6 to 12 carbon atoms, from 8 to 24 carbon atoms, from 8 to 18 carbon atoms, or from 8 to 12 carbon atoms;

[0447] R6is present as hydrogen; p is 1 ; t is 3; q is 1 ; and

[0448] X” is selected from hydroxide, carboxylate, halide, sulfate, organic sulfate, and organic sulfonate (e.g., is selected from acetate, acrylate, methacrylate, methylsulfate or ethylsulfate).

[0449] Embodiment 91. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) according to formula (14) is the reaction product of (i) an N,N-dialkylaminoalkylamine of formula HN(R6)-R4-N(R1)(R2) with (ii) a fatty acid of formula R5-C00H, an ester of a fatty acid of formula R5-C00H with an alcohol having from 1 to 4 carbon atoms, or a fatty acid triglyceride.

[0450] Embodiment 92. The method according to any non-inconsistent previous embodiment, wherein the dialkylamino group of the N,N dialkylaminoalkylamine either includes two alkyl groups independently selected from methyl, ethyl, propyl, and butyl, or R1and R2, together with the nitrogen atom to which they are attached, form a 5- or 6-membered heterocycle.

[0451] Embodiment 93. The method according to any non-inconsistent previous embodiment, wherein the N,N dialkylaminoalkylamine is selected from N,N dimethylaminoethylamine, N,N dimethylaminopropylamine, N,N diethylaminoethylamine, N,N diethylaminopropylamine, N,N dipropylaminoethylamine, N,N dipropylaminopropylamine, N,N dibutylaminoethylamine, N,N dibutylaminopropylamine, N,N dimethylaminopropylenediamine, N,N dipropylaminopropylenediamine, N,N dibutylaminopropylenediamine, N-(3-aminopropyl)pyrrolidine, N-(3- aminopropyl)piperidine, and N-(3-aminopropyl)azepane.

[0452] Embodiment 94. The method according to any non-inconsistent previous embodiment, wherein the fatty acid, fatty acid ester, or the fatty acid triglyceride is derived from a plant source, such as vegetable oils, or from an animal source, such as tallow oil, or combinations thereof. Embodiment 95. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) according to formula (14) is the reaction product of an amine selected from 3-(dialkylamino)propylamine and 2- (dialkylamino)ethylamine with vegetable oil or tallow oil.

[0453] Embodiment 96. The method according to any non-inconsistent previous embodiment, wherein the reaction product of (i) an N,N-dialkylaminoalkylamine with (ii) a fatty acid, a fatty acid ester, or a fatty acid triglyceride is neutralized with an acid or by quaternized with an alkylating agent.

[0454] Embodiment 97. The method according to any non-inconsistent previous embodiment, wherein the acid is selected from formic acid, acetic acid, chloroacetic acid, propionic acid, acrylic acid, and methacrylic acid.

[0455] Embodiment 98. The method according to any non-inconsistent previous embodiment, wherein the alkylating agent is an organic halide, the alkylating agent is an alkyl halide having from 1 to 8 carbon atoms.

[0456] Embodiment 99. The method according to any non-inconsistent previous embodiment wherein the amphiphile (A) is of the formula (15), (16), or (17), wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or R1and R2, together with the nitrogen to which they are attached, form a heterocycle;

[0457] R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2 position;

[0458] R4is -(CH2)t-, wherein t is 2, 3 or 4;

[0459] R5is a hydrocarbyl group having from 6 to 24 carbon atoms;

[0460] R6is hydrogen or an alkyl group having from 1 to 5 carbon atoms;

[0461] R7is hydrogen or an organic moiety having from 1 to 20 carbon atoms; each of R8and R9is hydrogen or an alkyl group having from 1 to 5 carbon atoms;

[0462] X” is an anion; and q is 0, 1 , or 2.

[0463] Embodiment 100. The method according to any non-inconsistent previous embodiment, wherein t is 3.

[0464] Embodiment 101. The method according to any non-inconsistent previous embodiment, wherein R6is an alkyl group having from 2 to 4 carbon atoms.

[0465] Embodiment 102. The method according to any non-inconsistent previous embodiment, wherein R7is an alkyl group having from 1 to 20 carbon atoms.

[0466] Embodiment 103. The method according to any non-inconsistent previous embodiment, wherein R9is an alkyl group having from 2 to 4 carbon atoms. Embodiment 104. The method according to any non-inconsistent previous embodiment, wherein R9is a methyl or a butyl group.

[0467] Embodiment 105. The method according to any non-inconsistent previous embodiment, wherein R8is an alkyl group having from 2 to 4 carbon atoms.

[0468] Embodiment 106. The method according to any non-inconsistent previous embodiment, wherein R8is a methyl or a butyl group.

[0469] Embodiment 107. The method according to any non-inconsistent previous embodiment, wherein q is 0.

[0470] Embodiment 108. The method according to any non-inconsistent previous embodiment, wherein q is 1 or 2.

[0471] Embodiment 109. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) is the reaction product of (i) a N,N dialkylaminoalkylamine having the general formula HN(R6)-R4-N(R1)(R2) with (ii) a first intermediate formed as the reaction product of one or more ethylenically unsaturated carboxylic acids or esters and an alkyl amine HN(R5)(R7).

[0472] Embodiment 110. The method according to any non-inconsistent previous embodiment, wherein the carboxylic acids or esters are an alkyl alkenoate, an alkyl acrylate, an alkenoic acid, or any combination thereof.

[0473] Embodiment 111. The method according to any non-inconsistent previous embodiment, wherein cocoylamine or oleylamine is first reacted with methyl acrylate and the reaction product is further reacted with a N,N dialkylaminoalkylamine to form an amide.

[0474] Embodiment 112. The method according to any non-inconsistent previous embodiment, wherein the N,N dialkylaminoalkylamine is selected from N,N- dimethylaminopropylamine, N,N dibutylaminopropylamine, and pyrrolidine. Embodiment 113. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) is the reaction product of an alkyl amine of the formula N(R5)(R7) with a first intermediate formed as the reaction product of one or more ethylenically unsaturated carboxylic acids or esters and a N,N dialkylamine. Embodiment 114. The method according to any non-inconsistent previous embodiment, wherein the N,N dialkylamine has the general formula H[N(R6)- R4]pN(R1)(R2).

[0475] Embodiment 115. The method according to any non-inconsistent previous embodiment, wherein p is 0 and the N,N dialkylamine is a secondary amine of the formula HN(R1)(R2).

[0476] Embodiment 116. The method according to any non-inconsistent previous embodiment, wherein the N,N dialkylamine is dimethylamine or dibutylamine.

[0477] Embodiment 117. The method according to any non-inconsistent previous embodiment, wherein p is 1 and the N,N dialkylamine is an N,N- dialkylaminoalkylamine of the formula HN(R6)-R4-N(R1)(R2).

[0478] Embodiment 118. The method according to any non-inconsistent previous embodiment, wherein the N,N-dialkylaminoalkylamine is N,N- dimethylaminopropylamine, N,N dibutylaminopropylamine, or pyrrolidine.

[0479] Embodiment 119. The method according to any non-inconsistent previous embodiment, wherein the N,N-dialkylaminoalkylamine is reacted with methyl acrylate to form an intermediate reaction product which is then reacted with an alkyl amine of the formula N(R5)(R7), to form an amide.

[0480] Embodiment 120. The method according to any non-inconsistent previous embodiment, wherein the alkyl amine of the formula N(R5)(R7) is a primary or secondary fatty amine derived from one or more fatty acids or fatty esters having from 6 to 24 carbon atoms. Embodiment 121. The method according to any non-inconsistent previous embodiment, wherein the one or more fatty acids or fatty esters are derived from corn oil, canola oil, coconut oil, safflower oil, sesame oil, palm oil, cottonseed oil, soybean oil, olive oil, sunflower oil, hemp oil, wheat germ oil, palm kernel oil, vegetable oil, caprylic acid, capric acid, lauric acid, stearic acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, sapienic acid, elaidic acid, vaccenic acid, linoleic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, behenic acid, lignoceric acid, cerotic acid, or oleic acids.

[0481] Embodiment 122. The method according to any non-inconsistent previous embodiment, wherein the alkyl amine of the formula N(R5)(R7) is a synthetic primary or secondary amine including selected from hexylamine, octylamine, dodecylamine, tridecylamine, tetradecylamine, N-methyldodecylamine, N-methyloctylamine, and didodecylamine.

[0482] Embodiment 123. The method according to any non-inconsistent previous embodiment, wherein the alkyl amine of the formula N(R5)(R7) is cocoylamine or oleylamine.

[0483] Embodiment 124. The method according to any non-inconsistent previous embodiment, wherein the amide is further reacted with an acid or an alkylating agent to form the amphiphile (A) according to formula (15), (16), or (17).

[0484] Embodiment 125. The method according to any non-inconsistent previous embodiment, wherein the at least one amphiphile (A) comprises a single amphiphile or a mixture of two or more amphiphiles.

[0485] Embodiment 126. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) includes (or is) one or more selected from an imidazoline of the general formula (19a), a quaternary imidazolinium salt of the general formula (19b), and a quaternary imidazolinium salt of the general formula (19c),

[0486] (19a) (19b) (19c) wherein

[0487] R11is an alkyl group having from 9 to 19 carbon atoms or is an alkenyl group having from 9 to 19 carbon atoms and 1 to 3 carbon-carbon double bonds;

[0488] R12is an optionally substituted alkyl group having from 1 to 18 carbon atoms, or is a nitrogen-containing heteroaliphatic group;

[0489] R13is selected from an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, and a benzyl group; and

[0490] Y” is an anion.

[0491] Embodiment 127. The method according to any not-inconsistent previous embodiment, wherein the at least one surfactant (B) includes (or is) one or more selected from an imidazoline of the general formula (19a).

[0492] Embodiment 128. The method according to any not-inconsistent previous embodiment, wherein the at least one surfactant (B) includes (or is) one or more selected from an imidazoline of the general formula (19b).

[0493] Embodiment 129. The method according to any not-inconsistent previous embodiment, wherein the at least one surfactant (B) includes (or is) one or more selected from an imidazoline of the general formula (19c).

[0494] Embodiment 130. The method according to any non-inconsistent previous embodiment, wherein R11has from 9 to 17, from 11 to 19, or from 11 to 17 carbon atoms. Embodiment 131. The method according to any non-inconsistent previous embodiment, wherein R11is a linear or branched alkyl group.

[0495] Embodiment 132. The method according to any non-inconsistent previous embodiment, wherein R11is an alkyl group derived from a saturated fatty acid.

[0496] Embodiment 133. The method according to any non-inconsistent previous embodiment, wherein R11is an alkyl group derived from an unsaturated fatty acid.

[0497] Embodiment 134. The method according to any non-inconsistent previous embodiment, wherein R11is selected from an alkenyl group having 17 carbon atoms and one carbon-carbon double bond, an alkenyl group having 17 carbon atoms and two carbon-carbon double bonds, and an alkenyl group having 17 carbon atoms and three carbon-carbon double bonds.

[0498] Embodiment 135. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) comprises a mixture of imidazoline or imidazolinium salts wherein some R11groups are alkyl groups derived from saturated fatty acids and some R11groups are alkenyl groups derived from unsaturated fatty acids.

[0499] Embodiment 136. The method according to any non-inconsistent previous embodiment, wherein the R11groups that are alkyl groups derived from saturated fatty acids are present in an amount of from 5 to 60 mol-%, from 15 to 60 mol-%, from 20 to 60 mol-%, from 5 to 40 mol-%, from 15 to 40 mol %, from 20 to 40 mol- %, from 5 to 20 mol-%, from 15 to 20 mol-%, from 5 to 10 mol-%, or from 1 to 10 mol-%, based on the total amount of imidazolines and imidazolinium salts in the mixture.

[0500] Embodiment 137. The method according to any non-inconsistent previous embodiment, wherein R12is an alkyl group having from 1 to 16, from 1 to 12, from 1 to 6, from 2 to 16, from 2 to 12, or from 2 to 6 carbon atoms. Embodiment 138. The method according to any non-inconsistent previous embodiment, wherein R12is selected from methyl, ethyl, propyl, butyl, pentyl, and dodecyl.

[0501] Embodiment 139. The method according to any non-inconsistent previous embodiment, wherein R12is a hydroxyalkyl group having from 1 to 16, from 1 to 12, from 1 to 6, from 2 to 16, from 2 to 12, from 2 to 6, or from 2 or 3 carbon atoms.

[0502] Embodiment 140. The method according to any non-inconsistent previous embodiment, wherein R12is selected from hydroxyethyl and hydroxypropyl.

[0503] Embodiment 141. The method according to any non-inconsistent previous embodiment, wherein R12is hydroxyethyl.

[0504] Embodiment 142. The method according to any non-inconsistent previous embodiment, wherein R12is an aminoalkylene group, a polyaminoalkylene group, or an ammoniumalkylene group.

[0505] Embodiment 143. The method according to any non-inconsistent previous embodiment, wherein the aminoalkylene group, polyaminoalkylene group, or ammoniumalkylene group has from 2 to 20 carbon atoms and from 1 to 10 nitrogen atoms.

[0506] Embodiment 144. The method according to any non-inconsistent previous embodiment, wherein one or more of the nitrogen atoms of the aminoalkylene group, polyaminoalkylene group, or ammoniumalkylene group are alkylated or acylated.

[0507] Embodiment 145. The method according to any non-inconsistent previous embodiment, wherein the aminoalkylene group, polyaminoalkylene group, or ammoniumalkylene group is linear or branched. Embodiment 146. The method according to any non-inconsistent previous embodiment, wherein R12is an aminoalkylene or polyaminoalkylene group of the formula (20a) or is an ammoniumalkylene group of the structural formula (20b),

[0508] {(CH2)r-[NR14-(CH2)s]t-NR15R16} (20a)

[0509] {(CH2)r-[NR14R18-(CH2)s]t-NR15R16R18}v+(20b) vY“ wherein,

[0510] R14is hydrogen or an optionally substituted hydrocarbyl residue having from 1 to 20 carbon atoms;

[0511] R15is hydrogen or an optionally substituted hydrocarbyl residue having from 1 to 20 carbon atoms;

[0512] R16is selected, independently from R15, from hydrogen, an optionally substituted hydrocarbyl residue having 1 to 20 carbon atoms, and an acyl group having the formula -C(=O)R17, with the proviso that R15and R16together may form a 5- or 6-membered ring,

[0513] R17is hydrogen or a Ci-Ci8hydrocarbyl group;

[0514] R18is hydrogen, an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, or a benzyl group; r and s are each, independently, 2 or 3; t is 0 or an integer from 1 to 10; v is 0 or an integer between 1 and 11 ; and

[0515] Y" is an anion.

[0516] Embodiment 147. The method according to any non-inconsistent previous embodiment, wherein R12is an aminoalkylene group or an N-substituted aminoalkylene and t is 0.

[0517] Embodiment 148. The method according to any non-inconsistent previous embodiment, wherein r is 2. Embodiment 149. The method according to any non-inconsistent previous embodiment, wherein R12is selected from aminoethyl, aminopropyl, N-methyl aminoethyl, N-ethyl aminoethyl, N-propyl aminoethyl, N-butyl aminoethyl, N,N- dimethyl aminoethyl, N,N-diethyl aminoethyl, N,N-dipropyl aminoethyl, and N,N- dibutyl aminoethyl.

[0518] Embodiment 150. The method according to any non-inconsistent previous embodiment, wherein R12is a polyaminoalkylene group and t is an integer from 1 to 6 or from 1 to 4.

[0519] Embodiment 151. The method according to any non-inconsistent previous embodiment, wherein t is 1 , 2, or 3.

[0520] Embodiment 152. The method according to any non-inconsistent previous embodiment, wherein r and s are both 2.

[0521] Embodiment 153. The method according to any non-inconsistent previous embodiment, wherein R12is selected from N-(2-aminoethyl)aminoethyl, N-(2- aminoethyl)aminopropyl, and higher homologues thereof.

[0522] Embodiment 154. The method according to any non-inconsistent previous embodiment, wherein R14is selected from hydrogen and hydrocarbyl groups having from 1 to 6 or from 1 to 3 carbon atoms.

[0523] Embodiment 155. The method according to any non-inconsistent previous embodiment, wherein R14is an alkyl group.

[0524] Embodiment 156. The method according to any non-inconsistent previous embodiment, wherein R14is selected from methyl, ethyl, and propyl.

[0525] Embodiment 157. The method according to any non-inconsistent previous embodiment, wherein R14is hydrogen. Embodiment 158. The method according to any non-inconsistent previous embodiment, wherein R15and R16are, independently, selected from hydrogen and an optionally substituted hydrocarbyl group.

[0526] Embodiment 159. The method according to any non-inconsistent previous embodiment, wherein R15and R16are the same.

[0527] Embodiment 160. The method according to any non-inconsistent previous embodiment, wherein R15and R16are different.

[0528] Embodiment 161. The method according to any non-inconsistent previous embodiment, wherein at least one of R15and R16is an optionally substituted hydrocarbyl group having from 1 to 14, from 1 to 6, or from 1 to 4 carbon atoms.

[0529] Embodiment 162. The method according to any non-inconsistent previous embodiment, wherein at least one of R15and R16is an alkyl group.

[0530] Embodiment 163. The method according to any non-inconsistent previous embodiment, wherein at least one of R15and R16is an alkyl group substituted with a hydroxyl group.

[0531] Embodiment 164. The method according to any non-inconsistent previous embodiment, wherein at least one of R15and R16is selected from methyl, ethyl, propyl, butyl, pentyl, and hydroxyethyl.

[0532] Embodiment 165. The method according to any non-inconsistent previous embodiment, wherein R15is hydrogen and R16is hydroxyethyl.

[0533] Embodiment 166. The method according to any non-inconsistent previous embodiment, wherein at least one of R15and R16is hydrogen and R16is an acyl group. Embodiment 167. The method according to any non-inconsistent previous embodiment, wherein R16is an acyl group having from 1 to 12, from 1 to 6, or from 1 to 4 carbon atoms.

[0534] Embodiment 168. The method according to any non-inconsistent previous embodiment, wherein R16is an acyl group derived from acetic acid, propionic acid, butyric acid, acrylic acid, or methacrylic acid.

[0535] Embodiment 169. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) includes a salt of the formula (19b) or (19c) and R13is an alkyl group having from 1 to 4 or from 1 or 2 carbon atoms.

[0536] Embodiment 170. The method according to any non-inconsistent previous embodiment, wherein R13is a hydroxyalkyl group having 2 or 3 carbon atoms.

[0537] Embodiment 171. The method according to any non-inconsistent previous embodiment, wherein R13is a hydroxyalkyl group having 2 carbon atoms.

[0538] Embodiment 172. The method according to any non-inconsistent previous embodiment, wherein R13is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and hydroxyethyl.

[0539] Embodiment 173. The method according to any non-inconsistent previous embodiment, wherein R13is selected from methyl, ethyl, and hydroxyethyl.

[0540] Embodiment 174. The method according to any non-inconsistent previous embodiment, wherein R13is ethyl.

[0541] Embodiment 175. The method according to any non-inconsistent previous embodiment, wherein one or both of R12and R13are hydroxyalkyl. Embodiment 176. The method according to any non-inconsistent previous embodiment, wherein the imidazoline of formula (19a) is formed by the reaction of a fatty acid with an N-substituted ethylene diamine under dehydrating conditions.

[0542] Embodiment 177. The method according to any non-inconsistent previous embodiment, wherein the fatty acid and the N-substituted ethylene diamine are reacted in a molar ratio of from 5:1 to 1 :5, from 2:1 to 1 :2, from 1.2 :1 to 1 :1.2, from 5:1 to 1 :2, from 5:1 to 1 :1.2, from 2:1 to 1 :5, from 2:1 to 1.2, from 1.2:1 to 1 :5, or from 1.2:1 to 1 :2.

[0543] Embodiment 178. The method according to any non-inconsistent previous embodiment, wherein the fatty acid has from 10 to 20 or from 12 to 18 carbon atoms.

[0544] Embodiment 179. The method according to any non-inconsistent previous embodiment, wherein the fatty acid is selected from oleic acid, linoleic acid, linolenic acid, and mixtures thereof.

[0545] Embodiment 180. The method according to any non-inconsistent previous embodiment, wherein the fatty acid is selected from lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof.

[0546] Embodiment 181. The method according to any non-inconsistent previous embodiment, wherein the fatty acid is selected from coconut oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid, and tallow fatty acid.

[0547] Embodiment 182. The method according to any non-inconsistent previous embodiment, wherein the fatty acid is tall oil fatty acid.

[0548] Embodiment 183. The method according to any non-inconsistent previous embodiment, wherein the N-substituted ethylene diamine is a polyamine having three or more amino groups. Embodiment 184. The method according to any non-inconsistent previous embodiment, wherein the N-substituted ethylene diamine is a polyamine having from 3 to 12 or from 3 to 6 amino groups.

[0549] Embodiment 185. The method according to any non-inconsistent previous embodiment, wherein the N-substituted ethylene diamine is a polyamine having 3, 4, 5, or 6 amino groups.

[0550] Embodiment 186. The method according to any non-inconsistent previous embodiment, wherein the N-substituted ethylene diamine is is selected from diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, and higher homologues thereof, such as heavy polyamines or polyamine bottoms.

[0551] Embodiment 187. The method according to any non-inconsistent previous embodiment, wherein the N-substituted ethylene diamine (ii) is a N-alkylated ethylene diamine selected from N'-methylethane-1 ,2-diamine, N'-ethylethane-1 ,2- diamine, N'-butylethane-1 ,2-diamine, N'-octadecylethane-1 ,2-diamine, 2-(2- aminoethylamino)ethanol N'-[2-(methylamino)ethyl]ethane-1 ,2-diamine, N’-[2-(ethylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(butylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(dimethylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(diethylamino)ethyl]ethane-1 ,2-diamine, N'-[2-(dibutylamino)ethyl]ethane-1 ,2-diamine, 2-[2-(2-aminoethylamino)ethylamino]ethanol, and mixtures thereof.

[0552] Embodiment 188. The method according to any non-inconsistent previous embodiment, wherein the N-substituted ethylene diamine (ii) has the general formula (21 )

[0553] H2N-(CH2)2-NH-R12(21 ) wherein R12is an optionally substituted alkyl group having from 1 to 18 carbon atoms, or is a nitrogen-containing heteroaliphatic group.

[0554] Embodiment 189. The method according to any non-inconsistent previous embodiment, wherein, the N-substituted ethylene diamine is an amino alkylethanolamine.

[0555] Embodiment 190. The method according to any non-inconsistent previous embodiment, wherein the N-substituted ethylene diamine contains a cyclic structure, wherein R15and R16, together with the nitrogen atom to which they are attached, form a 5- or 6-membered ring.

[0556] Embodiment 191. The method according to any non-inconsistent previous embodiment, wherein the 5- or 6-membered ring is an imidazoline or a piperazine structure.

[0557] Embodiment 192. The method according to any non-inconsistent previous embodiment, wherein the imidazoline formed by the reaction of the fatty acid with the N-substituted ethylene diamine is further reacted with a quaternizing agent.

[0558] Embodiment 193. The method according to any non-inconsistent previous embodiment, wherein the quaternizing agent converts some of or all the secondary and tertiary amino groups to quaternary ammonium groups.

[0559] Embodiment 194. The method according to any non-inconsistent previous embodiment, wherein the imidazoline is quaternized once to give an imidazolinium salt.

[0560] Embodiment 195. The method according to any non-inconsistent previous embodiment, wherein the quaternizing agent is an alkylating agent.

[0561] Embodiment 196. The method according to any non-inconsistent previous embodiment, wherein the quaternizing agent is alkylhalogenide, such as methylchloride, ethylchloride, propylchloride, butylchloride, benzylchloride, methylbromide, ethylbromide, propylbromide, butylbromide, benzylbromide; a dialkylsulfate, such as dimethylsulfate, diethylsulfate, dipropylsulfate and dibutylsulfate; or a dialkylcarbonate, such as dimethylcarbonate and diethylcarbonate.

[0562] Embodiment 197. The method according to any non-inconsistent previous embodiment, wherein the quaternizing agent does not contain a halogenide.

[0563] Embodiment 198. The method according to any non-inconsistent previous embodiment, wherein the imidazoline of the formula (19a) is reacted with a quaternizing agent.

[0564] Embodiment 199. The method according to any non-inconsistent previous embodiment, wherein the quaternizing agent adds substituent R13to the nitrogen atom in the 1 -position of the imidazoline of formula (19a) to provide the imidazolinium salt of formula (19b) or to the nitrogen atom in the 3-position of the imidazoline of formula (19a) to provide the imidazolinium salt of formula (19c).

[0565] Embodiment 200. The method according to any non-inconsistent previous embodiment, wherein Y- is selected from halides, sulfate, organic sulfates, carbonate, organic carbonates, phosphate, nitrate, and carboxylates, and any mixture thereof.

[0566] Embodiment 201. The method according to any non-inconsistent previous embodiment, wherein Y’ is sulfate.

[0567] Embodiment 202. The method according to any non-inconsistent previous embodiment, wherein Y’ is a halide selected from chloride, bromide, and iodide.

[0568] Embodiment 203. The method according to any non-inconsistent previous embodiment, wherein Y’ is an organic sulfate selected from CH3SO4 , C2H5SO4; CsHySCM', and C4HgSO4‘. Embodiment 204. The method according to any non-inconsistent previous embodiment, wherein Y’ is an organic carbonate selected from CH3-O-COO and CH2H5-O-COO-.

[0569] Embodiment 205. The method according to any non-inconsistent previous embodiment, wherein Y- is a carboxylate selected from acetate, propionate, butylate, acrylate, and methacrylate.

[0570] Embodiment 206. The method according to any non-inconsistent previous embodiment, wherein Y- is selected from Cl; CH3SO4 , C2H5SO4 C3H7SO4 and any mixture thereof.

[0571] Embodiment 207. The method according to any non-inconsistent previous embodiment, wherein Y’ is selected from CH3SO4; C2H5SO4; C3H7SO4; and any mixture thereof.

[0572] Embodiment 208. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) includes an imidazoline of the formula (19a) formed by the reaction of tall oil fatty acid with aminoethylethanolamine or tetraethylenepentamine.

[0573] Embodiment 209. The method according to any non-inconsistent previous embodiment, wherein the the at least one surfactant (B) includes a quaternary imidazolinium salt of the formula (19b) or (19c) formed by the reaction of tall oil fatty acid with aminoethylethanolamine or tetraethylenepentamine, followed by quaternization with a dialkylsulfate selected from dimethylsulfate, diethylsulfate, dipropylsulfate and dibutylsulfate.

[0574] Embodiment 210. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) includes an imidazoline of the formula (19a) wherein R11is an alkenyl group having 17 carbon atoms and 1 or 2 carbon-carbon double bonds; and

[0575] R12is a hydroxyethyl group.

[0576] Embodiment 211. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) includes a quaternary imidazolinium salt of the formula (19b) or (19c), wherein

[0577] R11is an alkenyl group having 17 carbon atoms and 1 or 2 carbon-carbon double bonds;

[0578] R12is a hydroxyethyl group;

[0579] R13is ethyl.

[0580] Embodiment 212. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) includes one or more selected from 2-oleyl-N-methyl imidazoline quaternized with methylchloride, 2-oleyl-N- hydroxyethyl imidazoline quaternized with methylbromide, 2-oleyl-N-hydroxyethyl imidazoline quaternized with diethylsulfate, 2-oleyl-N-butyl-imidazoline quaternized with diethylsulfate, 2-linoleyl-N -hydroxyethyl imidazoline quaternized with dimethylsulfate, 2-tallyl-N-N’-aminoethyl imidazoline with methylchloride.

[0581] Embodiment 213. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio range of from 95:5 to 5:95, from 85:15 to 15:85, from 75:25 to 25:75, from 70:30 to 30:70, from 65:35 to 35:65, from 60:40 to 40:60, or from 55:45 to 45:55.

[0582] Embodiment 214. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio range of from 3:1 to 1 :3, from 4:1 to 1 :4, from 5:2 to 2:5, from 3:2 to 2:3, or from 1 :2 to 2:1.

[0583] Embodiment 215. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio range of from 95:5 to 50:50, e.g., from 95:5 to 60:40, or from 95:50 to 70:30, or from 90:10 to 50:50, or from 90:10 to 60:40, or from 90:10 to 70:30.

[0584] Embodiment 216. The method according to any non-inconsistent previous embodiment, wherein the amphiphile (A) is present in an amount of from 5 to 95 wt.- %, from 5 to 85 wt.-%, from 5 to 75 wt.-%, from 5 to 65 wt.-%, from 5 to 60 wt.-%, from 5 to 55 wt.-%, from 5 to 50 wt.-%, 15 to 95 wt.-%, from 15 to 85 wt.-%, from 15 to 75 wt.-%, from 15 to 65 wt.-%, from 15 to 60 wt.-%, from 15 to 55 wt.-%, from 15 to 50 wt.-%, 25 to 95 wt.-%, from 25 to 85 wt.-%, from 25 to 75 wt.-%, from 25 to 65 wt.-%, from 25 to 60 wt.-%, from 25 to 55 wt.-%, from 25 to 50 wt.-%, 35 to 95 wt.-%, from 35 to 85 wt.-%, from 35 to 75 wt.-%, from 35 to 65 wt.-%, from 35 to 60 wt.-%, from 35 to 55 wt.-%, from 35 to 50 wt.-%, 45 to 95 wt.-%, from 45 to 85 wt.- %, from 45 to 75 wt.-%, from 45 to 65 wt.-%, from 45 to 60 wt.-%, from 45 to 55 wt.- %, or from 45 to 50 wt.-%, based on the combined weights of (A) and (B).

[0585] Embodiment 217. The method according to any non-inconsistent previous embodiment, wherein the at least one surfactant (B) is present in an amount of 5 to 95 wt.-%, from 5 to 85 wt.-%, from 5 to 75 wt.-%, from 5 to 65 wt.-%, from 5 to 55 wt.-%, from 5 to 50 wt.-%, from 5 to 45 wt.-%, from 5 to 40 wt.-%, 15 to 95 wt.-%, from 15 to 85 wt.-%, from 15 to 75 wt.-%, from 15 to 65 wt.-%, from 15 to 55 wt.-%, from 15 to 50 wt.-%, from 15 to 45 wt.-%, from 15 to 40 wt.-%, 20 to 95 wt.-%, from 20 to 85 wt.-%, from 20 to 75 wt.-%, from 20 to 65 wt.-%, from 20 to 55 wt.-%, from 20 to 50 wt.-%, from 20 to 45 wt.-%, from 20 to 40 wt.-%, 25 to 95 wt.-%, from 25 to 85 wt.-%, from 25 to 75 wt.-%, from 25 to 65 wt.-%, from 25 to 55 wt.-%, from 25 to 50 wt.-%, from 25 to 45 wt.-%, from 25 to 40 wt.-%, 30 to 95 wt.-%, from 30 to 85 wt.-%, from 30 to 75 wt.-%, from 30 to 65 wt.-%, from 30 to 55 wt.-%, from 30 to 50 wt.-%, from 30 to 45 wt.-%, or from 30 to 40 wt.-%, based on the combined weights of (A) and (B).

[0586] Embodiment 218. The method according to any non-inconsistent previous embodiment, wherein a system containing hydrocarbons and water is brought into contact with an amphiphile (A), at least one surfactant (B), and at least one further surfactant (C).

[0587] Embodiment 219. The method according to any non-inconsistent previous embodiment, wherein the at least one further surfactant (C) is present in an amount of from 0.1 to 15 wt.-%, from 0.5 to 15 wt.-%, from 1 to 15 wt.-%, from 5 to 15 wt.- %, from 10 to 15 wt.-%, from 0.1 to 10 wt.-%, from 0.5 to 10 wt.-%, from 1 to 10 wt.- %, from 5 to 10 wt.-%, from 0.1 to 5 wt.-%, from 0.5 to 5 wt.-%, or from 1 to 5 wt.- %, based on the combined weight of the amphiphile (A) and the at least one surfactant (B).

[0588] Embodiment 220. The method according to any non-inconsistent previous embodiment, wherein the at least one further surfactant (C) is selected from anionic, nonionic, zwitterionic (amphoteric), and surfactants. In such embodiments, the at least one further surfactant (C) is different from the amphiphile (A) and the at least one surfactant (B).

[0589] Embodiment 221. The method according to any non-inconsistent previous embodiment, wherein the method is applied to fluids that contain various levels of oil, brine, or both, wherein the fluid has a salinity of about 0.8 to about 25 wt.-% or about 10 to about 25 wt.-%.

[0590] Embodiment 222. The method according to any non-inconsistent previous embodiment, wherein the method is applied to a hydrocarbon system containing a volume percent of water of from about 1 to about 90 vol.-%, from about 5 to about 90 vol.-%, from about 10 to about 90 vol.-%, from about 1 to about 85 vol.-%, from about 5 to about 85 vol.-%, from about 10 to about 85 vol.-%, from about 1 to about 80 vol.-%, from about 5 to about 80 vol.-%, from about 10 to about 80 vol.-%, from about 1 to about 75 vol.-%, from about 5 to about 75 vol.-%, from about 10 to about 75 vol.-%, from about 1 to about 70 vol.-%, from about 5 to 70 vol.-%, from about 10 to about 70 vol.-%, from about 1 to about 60 vol.-%, from about 5 to 60 vol.-%, from about 10 to about 60 vol.-%, from about 1 to about 50 vol.-%, from about 5 to 50 vol.-%, or from about 10 to about 50 vol.-%, with respect to the total volume of water and hydrocarbon phases.

[0591] Embodiment 223. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.001 wt%, e.g., at least 0.005 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0592] Embodiment 224. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.01 wt%, e.g., at least 0.05 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0593] Embodiment 225. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.1 wt%, e.g., at least 0.2 or at least 0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0594] Embodiment 226. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.4 wt%, e.g., at least 0.5 or at least 0.6 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water and hydrocarbon.

[0595] Embodiment 227. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is at least 0.7 wt%, e.g., at least 0.8 or at least 0.9 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. Embodiment 228. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is in the range of 0.001 wt%-8 wt%, e.g., in the range of 0.001 -2 wt%, or 0.001 -1 wt%, or 0.005-8 wt%, or 0.005-2 wt%, or 0.005-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0596] Embodiment 229. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is in the range of 0.01 wt%-8 wt%, e.g., in the range of 0.01 -2 wt%, or 0.01-1 wt%, or 0.05-8 wt%, or 0.05-2 wt%, or 0.05-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0597] Embodiment 230. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-8 wt%, e.g., in the range of 0.1 - 2 wt%, or 0.1 -1 wt%, or 0.2-8 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.3-8 wt%, or 0.3- 2 wt%, or 0.3-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0598] Embodiment 231. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is in the range of 0.4 wt%-8 wt%, e.g., in the range of 0.4- 2 wt%, or 0.4-1 wt%, or 0.5-8 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.6-8 wt%, or 0.6-2 wt%, or 0.6-1 .4 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0599] Embodiment 232. The method according to any non-inconsistent previous embodiment, wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is in the range of 0.7 wt%-8 wt%, e.g., in the range of 0.7- 2 wt%, or 0.7-1 .5 wt%, or 0.8-8 wt%, or 0.8-2 wt%, or 0.8-1 .6 wt%, or 0.9-8 wt%, or 0.9-2 wt%, or 0.9-17 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0600] Embodiment 233. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is at least 0.001 wt%, e.g., at least 0.005 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0601] Embodiment 234. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is at least 0.01 wt%, e.g., at least 0.05 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0602] Embodiment 235. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is at least 0.1 wt%, e.g., at least 0.2 or at least 0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0603] Embodiment 236. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is at least 0.4 wt%, e.g., at least 0.5 or at least 0.6 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0604] Embodiment 237. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is at least 0.7 wt%, e.g., at least 0.8 or at least 0.9 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0605] Embodiment 238. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.001 wt%-8 wt%, e.g., in the range of 0.001-2 wt%, or 0.001 - 1 wt%, or 0.005-8 wt%, or 0.005-2 wt%, or 0.005-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0606] Embodiment 239. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.01 wt%-8 wt%, e.g., in the range of 0.01 -2 wt%, or 0.01 -1 wt%, or 0.05-8 wt%, or 0.05-2 wt%, or 0.05-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0607] Embodiment 240. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-8 wt%, e.g., in the range of 0.1-2 wt%, or 0.1-1 wt%, or 0.2-8 wt%, or 0.2-2 wt%, or 0.2-1 wt%, or 0.3-8 wt%, or 0.3-2 wt%, or 0.3-1 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0608] Embodiment 241. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.4 wt%-8 wt%, e.g., in the range of 0.4-2 wt%, or 0.4-1 wt%, or 0.5-8 wt%, or 0.5-2 wt%, or 0.5-1 .2 wt%, or 0.6-8 wt%, or 0.6-2 wt%, or 0.6-1 .4 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0609] Embodiment 242. The method according to any non-inconsistent previous embodiment, wherein the concentration of (A) in the mixture of hydrocarbons and water is in the range of 0.7 wt%-8 wt%, e.g., in the range of 0.7-2 wt%, or 0.7-1.5 wt%, or 0.8-8 wt%, or 0.8-2 wt%, or 0.8-1 .6 wt%, or 0.9-8 wt%, or 0.9-2 wt%, or 0.9- 17 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0610] Embodiment 243. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is at least 0.001 wt%, e.g., at least 0.005 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0611] Embodiment 244. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is at least 0.01 wt%, e.g., at least 0.02 wt%, or at least 0.03 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0612] Embodiment 245. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is at least 0.04 wt%, e.g., at least 0.06 or at least 0.08 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0613] Embodiment 246. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is at least 0.1 wt%, e.g., at least 0.12 or at least 0.14 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0614] Embodiment 247. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is at least 0.16 wt%, e.g., at least 0.18 or at least 0.2 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0615] Embodiment 248. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.001 wt%-2 wt%, e.g., in the range of 0.001 -0.5 wt%, or 0.001-0.3 wt%, or 0.005-2 wt%, or 0.005-0.5 wt%, or 0.005-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon. Embodiment 249. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.01 wt%-2 wt%, e.g., in the range of 0.01-0.5 wt%, or 0.01 - 0.3 wt%, or 0.02-2 wt%, or 0.02-0.5 wt%, or 0.02-0.3 wt%, or 0.03-2 wt%, or 0.03- 0.5 wt%, or 0.03-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0616] Embodiment 250. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.04 wt%-2 wt%, e.g., in the range of 0.04-0.5 wt%, or 0.04- 0.3 wt%, or 0.06-2 wt%, or 0.06-0.5 wt%, or 0.06-0.3 wt%, or 0.08-2 wt%, or 0.08- 0.5 wt%, or 0.08-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0617] Embodiment 251. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-2 wt%, e.g., in the range of 0.1 -0.5 wt%, or 0.1 -0.3 wt%, or 0.12-2 wt%, or 0.12-0.5 wt%, or 0.12-0.3 wt%, or 0.14-2 wt%, or 0.14-0.5 wt%, or 0.14-0.3 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0618] Embodiment 252. The method according to any non-inconsistent previous embodiment, wherein the concentration of (B) in the mixture of hydrocarbons and water is in the range of 0.16 wt%-2 wt%, e.g., in the range of 0.16-0.5 wt%, or 0.16- 0.31 wt%, or 0.18-2 wt%, or 0.18-0.5 wt%, or 0.18-0.32 wt%, or 0.2-2 wt%, or 0.2- 0.5 wt%, or 0.2-0.35 wt%, relative to the total weight of the aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

[0619] Embodiment 253. The method according to any non-inconsistent previous embodiment, wherein, as compared to the total dose rate of either (A) or (B) individually, the total dose rate of (A) + (B) needed to prevent hydrate agglomeration may be reduced by from 10 to 70 wt.-%, from 10 to 60 wt.-%, from 10 to 50 wt.-%, from 10 to 40 wt.-%, 20 to 70 wt.-%, from 20 to 60 wt.-%, from 20 to 50 wt.-%, from

[0620] 20 to 40 wt.-%, from 30 to 70 wt.-%, from 30 to 60 wt.-%, from 30 to 50 wt.-%, from

[0621] 30 to 40 wt.-%, from 40 to 70 wt.-%, from 40 to 60 wt.-%, from 40 to 50 wt.-%, from

[0622] 50 to 70 wt.-%, or from 50 to 60 wt.-%.

[0623] Embodiment 254. The method according to any non-inconsistent previous embodiment, wherein, as compared to the total dose rate of either (A), (B), or (C) individually, the total dose rate of (A) + (B) + (C) needed to prevent hydrate agglomeration may be reduced by from 10 to 70 wt.-%, from 10 to 60 wt.-%, from

[0624] 10 to 50 wt.-%, from 10 to 40 wt.-%, 20 to 70 wt.-%, from 20 to 60 wt.-%, from 20 to

[0625] 50 wt.-%, from 20 to 40 wt.-%, from 30 to 70 wt.-%, from 30 to 60 wt.-%, from 30 to

[0626] 50 wt.-%, from 30 to 40 wt.-%, from 40 to 70 wt.-%, from 40 to 60 wt.-%, from 40 to

[0627] 50 wt.-%, from 50 to 70 wt.-%, or from 50 to 60 wt.-%.

[0628] Embodiment 255. A hydrate inhibitor composition comprising, an amphiphile (A) and at least one surfactant (B), wherein the amphiphile (A) and the at least one surfactant (B) are as defined in any of the previous embodiments.

[0629] Embodiment 256. The hydrate inhibitor composition according to embodiment 254 further comprising at least one further surfactant (C), wherein the at least one further surfactant (C) is as defined in any of the previous embodiments.

[0630] Embodiment 257. The hydrate inhibitor composition according to embodiment 254 or 255, wherein the amphiphile (A), the at least one surfactant (B), and, optionally, the at least one further surfactant (C) are present in an amount according to any of the previous embodiments.

[0631] Embodiment 258. The hydrate inhibitor composition according to embodiment 254 further comprising at least one further surfactant (C) selected from the group consisting of anionic, nonionic, amphoteric, and cationic surfactants, wherein the amphiphile (A) and the at least one further surfactant (C) are present in a weight-to- weight ratio (A):(C) of from 1 :1 to 4:1. Embodiment 259. A formulation comprising an amphiphile (A), at least one surfactant (B), and, optionally, at least one further surfactant (C), wherein the amphiphile (A), the at least one surfactant (B), and, optionally, the at least one further surfactant (C) are as defined in any previous embodiment.

[0632] Embodiment 260. The formulation according to embodiment 258, wherein the amphiphile (A), the at least one surfactant (B), and, optionally, the at least one further surfactant (C) are present in an amount according to any of the previous embodiments.

[0633] Embodiment 261. The formulation according to embodiment 258 or 259, wherein the formulation further comprises a diluent.

[0634] Embodiment 262. The formulation according to embodiment 260, wherein the concentration of the diluent is from about 1 to about 95 wt.-%, from about 1 to about 90 wt.-%, from about 1 to about 80 wt.-%, from about 10 to about 95 wt.-%, from about 10 to about 90 wt.-%, from about 10 to about 80 wt.-%, from about 20 to about 95 wt.-%, from about 20 to about 90 wt.-%, or from about 20 to about 80 %, based on the weight of the formulation comprising (A), (B), optionally (C), and the diluent.

[0635] Embodiment 263. The formulation according to embodiment 260 comprising from 40 to 75 wt.-% of (A), (B), and, optionally, (C) and from 25 to 60 wt.-% of a solvent.

Claims

CLAIMSWhat is claimed is:1 . A method for inhibiting the formation of gas hydrate agglomerates and / or plugs, the method comprising bringing a system containing hydrocarbons and water into contact with at least one amphiphile (A) each of the formula (1a) or (1 b) R5-L-N(R1)(R2) (1 a)[R5— L— N(R1)(R2)(R3)]q+[X-]q(1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or R1and R2, together with the nitrogen to which they are attached, form a heterocycle;R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from the group consisting of nitrogen and oxygen, and optionally one or more further heteroatoms;R5is a hydrocarbyl group having from 6 to 24 carbon atoms; X’ is an anion; and q is 0 or an integer from 1 to 7; and at least one surfactant (B) each comprising an imidazoline head group and a C9-C19 linear hydrocarbyl tail, wherein the at least one amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) of from 95:5 to 5:95.

2. The method according to claim 1 , wherein the at least one amphiphile (A) comprises an amphiphile of the formula (1 b), wherein each of R1and R2is, independently, an alkyl group having 3, 4, or 5 carbon atoms;R3is hydrogen;R5is a mixture of hexadecenyl, octadecenyl, and eicosenyl; q is 1 ; andX” is selected from the group consisting of acetate, halide, acrylate, and methacrylate.

3. The method according to claim 1 , wherein the linking moiety L is selected from the group consisting of the chemical structures (2) to (12):-C(=O)-N(R6)-(CH2)t- (2)-N(R7)-C(=O)-(CH2)t- (3)-N(R7)-(CH2)2-C(=O)-NH-(CH2)t- (4)-N(R7)-C(=O)-(CH2)2-N(R6)-(CH2)t- (5)-CH(OH)-CH2-N(R6)-(CH2)t- (6)-CH(COOH)-CH2-C(=O)-N(R6)-(CH2)t- (7a)-CH(CH2-COOH)-C(=O)-N(R6)-(CH2)t- (7b)-CH(COOH)-CH2-C(=O)-[O-(CH2)t]v- (8a)-CH(CH2-COOH)-C(=O)-[O-(CH2)t]v- (8b)-N(R7)-C(=O)-(CH2)2-C(=O)-N(R6)-(CH2)t- (9)-N(R7)-C(=O)-CH2-CH(OH)-C(=O)-N(R6)-(CH2)t- (10a)-N(R7)-C(=O)-CH(OH)-CH2-C(=O)-N(R6)-(CH2)t- (10b)-N(R7)-C(=O)-CH(OH)-CH(OH)-C(=O)-N(R6)-(CH2)t- (11 )-N(R7)-C(=O)-C(OH)(CH2COOH)-CH2-C(=O)-N(R6)-(CH2)t- (12a)-N(R7)-C(=O)-CH2-C(OH)(CH2COOH)-C(=O)-N(R6)-(CH2)t- (12b)4. The method according to claim 1 , wherein the at least one surfactant (B) comprises one or more selected from the group consisting of an imidazoline of thegeneral formula (19a), a quaternary imidazolinium salt of the general formula (19b), and a quaternary imidazolinium salt of the general formula (19c),(19a) (19b) (19c) whereinR11is an alkyl group having from 9 to 19 carbon atoms or is an alkenyl group having from 9 to 19 carbon atoms and 1 to 3 carbon-carbon double bonds;R12is an optionally substituted alkyl group having from 1 to 18 carbon atoms, or is a nitrogen-containing heteroaliphatic group;R13is selected from the group consisting of an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, and a benzyl group; andY” is an anion.

5. The method according to claim 4, wherein the at least one surfactant (B) comprises a mixture of imidazoline or imidazolinium salts wherein some R11groups are alkyl groups derived from saturated fatty acids and some R11groups are alkenyl groups derived from unsaturated fatty acids; and the R12groups are hydroxyalkyl groups having from 1 to 16 carbon atoms.

6. The method according to claim 4, wherein R12is selected from hydroxyethyl and hydroxypropyl.

7. The method according to claim 4, wherein the at least one surfactant (B) includes a salt of the formula (19b) or (19c);R13is an alkyl group having from 1 to 4 carbon atoms; andY’ is selected from halides, sulfate, organic sulfates, carbonate, organic carbonates, phosphate, nitrate, and carboxylates, and any mixture thereof.

8. The method according to claim 4, wherein the at least one surfactant (B) includes an imidazoline of formula (19a) that is formed by the reaction of a fatty acid with an N-substituted ethylene diamine under dehydrating conditions, wherein the fatty acid is selected from the group consisting of coconut oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid, and tallow fatty acid; and the N-substituted ethylene diamine has the general formula (21 )H2N-(CH2)2-NH-R12(21 ) wherein R12is an optionally substituted alkyl group having from 1 to 18 carbon atoms or is a nitrogen-containing heteroaliphatic group.

9. The method according to claim 4, wherein the at least one surfactant (B) includes a quaternary imidazolinium salt of the formula (19b) or (19c) formed by the reaction of tall oil fatty acid with aminoethylethanolamine or tetraethylenepentamine, followed by quaternization with a dialkylsulfate selected from dimethylsulfate, diethylsulfate, dipropylsulfate and dibutylsulfate.

10. The method according to claim 1 , wherein the amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio range of from 95:5 to 50:50 or from 80:20 to 20:80.11 . The method according to claim 1 , wherein the system containing hydrocarbons and water is brought into contact with the amphiphile (A), the at least one surfactant (B), and at least one further surfactant (C).

12. The method according to claim 11 , wherein the at least one further surfactant (C) is selected from the group consisting of anionic, nonionic, amphoteric, and cationic surfactants.; and the amphiphile (A) and the at least one further surfactant (C) are present in a weight-to-weight ratio (A):(C) of from 1 :1 to 4:1.

13. The method according to claim 1 , wherein the combined concentration of (A) and (B) in the mixture of hydrocarbons and water is in the range of 0.1 wt%-8 wt%, relative to the total weight of an aqueous phase that is part of the mixture of fluids, water, and hydrocarbon.

14. A hydrate inhibitor composition comprising at least one amphiphile (A) each of the formula (1a) or (1 b) R5-L-N(R1)(R2) (1 a)[R5— L— N(R1)(R2)(R3)]q+[X-]q(1 b) wherein each of R1and R2is, independently, an alkyl group having from 1 to 5 carbon atoms; or R1and R2, together with the nitrogen to which they are attached, form a heterocycle;R3is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxyl group or a carboxy group at the 2-position;L is a linking moiety comprising an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from the group consisting of nitrogen and oxygen, and optionally one or more further heteroatoms;R5is a hydrocarbyl group having from 6 to 24 carbon atoms;X’ is an anion; and q is 0 or an integer from 1 to 7; at least one surfactant (B) each comprising an imidazoline head group and aC9-C19 linear hydrocarbyl tail; andwherein the at least one amphiphile (A) and the at least one surfactant (B) are present in a weight-to-weight ratio (A):(B) of from 95:5 to 50:50 or from 80:20 to 20:80.

15. The hydrate inhibitor composition according to claim 14, wherein the at least one amphiphile (A) comprises an amphiphile of the formula (1 b), wherein each of Ri and R2 is, independently, an alkyl group having 3, 4, or 5 carbon atoms;R3 is hydrogen;R5is a mixture of hexadecenyl, octadecenyl, and eicosenyl; q is 1 ;X” is selected from the group consisting of acetate, halide, acrylate, and methacrylate; and the linking moiety L is selected from the group consisting of the chemical structures (2) to (12):-C(=O)-N(R6)-(CH2)t- (2)-N(R7)-C(=O)-(CH2)t- (3)-N(R7)-(CH2)2-C(=O)-NH-(CH2)t- (4)-N(R7)-C(=O)-(CH2)2-N(R6)-(CH2)t- (5)-CH(OH)-CH2-N(R6)-(CH2)t- (6)-CH(COOH)-CH2-C(=O)-N(R6)-(CH2)t- (7a)-CH(CH2-COOH)-C(=O)-N(R6)-(CH2)t- (7b)-CH(COOH)-CH2-C(=O)-[O-(CH2)t]v- (8a)-CH(CH2-COOH)-C(=O)-[O-(CH2)t]v- (8b)-N(R7)-C(=O)-(CH2)2-C(=O)-N(R6)-(CH2)t- (9)-N(R7)-C(=O)-CH2-CH(OH)-C(=O)-N(R6)-(CH2)t- (10a)-N(R7)-C(=O)-CH(OH)-CH2-C(=O)-N(R6)-(CH2)t- (10b)-N(R7)-C(=O)-CH(OH)-CH(OH)-C(=O)-N(R6)-(CH2)t- (11 )-N(R7)-C(=O)-C(OH)(CH2COOH)-CH2-C(=O)-N(R6)-(CH2)t- (12a)-N(R7)-C(=O)-CH2-C(OH)(CH2COOH)-C(=O)-N(R6)-(CH2)t- (12b)16. The hydrate inhibitor composition according to claim 14, wherein the at least one surfactant (B) comprises one or more selected from the group consisting of an imidazoline of the general formula (19a), a quaternary imidazolinium salt of the general formula (19b), and a quaternary imidazolinium salt of the general formula (19c),(19a) (19b) (19c) whereinR11is an alkyl group having from 9 to 19 carbon atoms or is an alkenyl group having from 9 to 19 carbon atoms and 1 to 3 carbon-carbon double bonds;R12is an optionally substituted alkyl group having from 1 to 18 carbon atoms, or is a nitrogen-containing heteroaliphatic group;R13is selected from the group consisting of an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group having from 2 to 4 carbon atoms, and a benzyl group; andY” is an anion.

17. The hydrate inhibitor composition according to claim 16, wherein R12is selected from hydroxyethyl and hydroxypropyl.

18. The hydrate inhibitor composition according to claim 16, wherein the at least one surfactant (B) includes a salt of the formula (19b) or (19c);R13is an alkyl group having from 1 to 4 carbon atoms; andY’ is selected from halides, sulfate, organic sulfates, carbonate, organic carbonates, phosphate, nitrate, and carboxylates, and any mixture thereof.

19. The hydrate inhibitor composition according to claim 16, wherein the at least one surfactant (B) includes an imidazoline of formula (19a) that is formed by the reaction of a fatty acid with an N-substituted ethylene diamine under dehydrating conditions, wherein the fatty acid is selected from the group consisting of coconut oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid, and tallow fatty acid; and the N-substituted ethylene diamine has the general formula (21 ) H2N-(CH2)2-NH-R12(21 ) wherein R12is an optionally substituted alkyl group having from 1 to 18 carbon atoms or is a nitrogen-containing heteroaliphatic group.

20. The hydrate inhibitor composition according to claim 14 further comprising at least one further surfactant (C) selected from the group consisting of anionic, nonionic, amphoteric, and cationic surfactants, wherein the amphiphile (A) and the at least one further surfactant (C) are present in a weight-to-weight ratio (A):(C) of from 1 :1 to 4: 1 .

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