PHASE TRANSFER CATALYST FOR BREAKING

EMULSIONS OF OIL IN WATER

BACKGROUND

[0001] The present disclosure relates to a phase transfer catalyst and the use thereof in resolving oil in water emulsions.

[0002] Conventional chemicals used to break emulsions include alkylphenol formaldehyde resin alkoxylates (AFRA), polyalkylene glycols (PAG), and organic sulfonates. These conventional chemicals can often be viscous, requiring solvents to reach a usable viscosity. In the production of olefins, feedstocks heavier than ethane, such as propane and butane, can create emulsion problems. In addition, the performance of conventional emulsion breaking chemicals can be less than ideal in some situations. For example, emulsions containing tar compounds can be particularly difficult to break.

[0003] Accordingly, there is an ongoing need for new, economical, and effective emulsion breaking chemicals and processes for resolving oil and water emulsions, particularly those containing tar compounds. Thus, there is a need to address these and other shortcomings associated with emulsion breaking chemicals and processes. These needs and other needs are satisfied by the compositions and methods of the present disclosure.

SUMMARY

[0004] In accordance with the purpose(s) of the invention, as embodied and broadly described herein, this disclosure, in some aspects, relates to a phase transfer catalyst and the use thereof in resolving oil in water emulsions.

[0005] In some aspects, the present disclosure provides a method for at least partially demulsifying an emulsion, the method comprising contacting the emulsion with a

composition comprising a monoquaternary ammonium salt, monoquaternary phosphonium salt, a bis-quaternary ammonium salt, a bis-quaternary phosphonium salt, or a combination thereof; wherein the mono-quaternary salt, if present, is represented by a general formula

wherein each of Ri _, R _2i R _3, and R4 are same or different and comprises an alkyl group, an aralkyl group, or a combination thereof, wherein A comprises nitrogen or phosphorus, and wherein X can comprise any ionic counter anion; wherein the bis-quaternary ammonium if present, is represented by a general formula

wherein each of Ri-R ₆ are the same or different and independently comprise from 1 to 12 carbons, an alkyl group, an aralkyl group, or a combination thereof; wherein each of Ai and A ₂ independently comprise nitrogen or phosphorus; wherein Z comprises a carbon-hydrogen chain, and wherein X comprises a counter anion.

DESCRIPTION

[0006] The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein.

[0007] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.

[0008] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a ketone" includes mixtures of two or more ketones.

[0009] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0010] As used herein, the terms "optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the phrase "optionally substituted alkyl" means that the alkyl group can or cannot be substituted and that the description includes both substituted and unsubstituted alkyl groups.

[0011] Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively

contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the invention.

[0012] References in the specification and concluding claims to parts by weight of a particular element or component in a composition or article denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0013] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0014] The term "alkyl group" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. A "lower alkyl" group is an alkyl group containing from one to six carbon atoms.

[0015] The term "alkoxy" as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy" group may be defined as -OR where R is alkyl as defined above. A "lower alkoxy" group is an alkoxy group containing from one to six carbon atoms.

[0016] The term "alkenyl group" as used herein is a hydrocarbon group of from 2 to 24 carbon atoms and structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (AB)C=C(CD) are intended to include both the E and Z isomers. This may be presumed in structural formulae herein wherein an asymmetric alkene is present, or it may be explicitly indicated by the bond symbol C.

[0017] The term "alkynyl group" as used herein is a hydrocarbon group of 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.

[0018] The term "aryl group" as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc. The term "aromatic" also includes "heteroaryl group," which is defined as an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy.

[0019] The term "cycloalkyl group" as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term

"heterocycloalkyl group" is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.

[0020] The term "aralkyl" as used herein is an aryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group. An example of an aralkyl group is a benzyl group.

[0021] The term "hydroxyalkyl group" as used herein is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with a hydroxyl group.

[0022] The term "alkoxyalkyl group" is defined as an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with an alkoxy group described above.

[0023] The term "ester" as used herein is represented by the formula— C(0)OA, where A can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.

[0024] The term "carbonate group" as used herein is represented by the

formula -OC(0)OR, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.

[0025] The term "carboxylic acid" as used herein is represented by the

formula -C(0)OH.

[0026] The term "aldehyde" as used herein is represented by the formula -C(0)H.

[0027] The term "keto group" as used herein is represented by the formula -C(0)R, where R is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.

[0028] The term "carbonyl group" as used herein is represented by the formula C=0.

[0029] The term "ether" as used herein is represented by the formula AOA ¹ , where A and A ¹ can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.

[0030] The term "sulfo-oxo group" as used herein is represented by the

formulas -S(0) ₂ R, -OS(0) ₂ R, or , -OS(0) ₂ OR, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.

[0031] Each of the materials disclosed herein are either commercially available and/or the methods for the production thereof are known to those of skill in the art. [0032] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

[0033] As briefly described above, the present disclosure provides a demulsifying agent that can, in various aspects, be useful in at least partially breaking an emulsion. As used herein, the term "break" is intended to refer to the separation of at least a portion of two or more components in an emulsion, for example, water and oil. In other aspects, the present disclosure provides methods for the use of such a demulsifying agent.

[0034] The compositions and methods described herein can be useful with a variety of emulsions and the present invention is not intended to be limited to any particular type of emulsion or components. Emulsions, such as, for example, emulsions of water and gasoline can be problematic to separate and can require the use of significant amounts of conventional demulsifying agents. In some aspects, the compositions and methods described herein can be useful in separating or at least partially separating an emulsion comprising an aqueous phase and an organic phase. In another aspect, the compositions and methods described herein can be useful in separating an emulsion of water and oil, an emulsion of water and gasoline, an emulsion of water and a hydrocarbons such as a petroleum based hydrocarbon or mixture of petroleum based hydrocarbons. In some aspects, oil and water emulsions from a cracker unit, for example, used in the production of olefins, can comprise a plurality of fine hydrocarbon (e.g., oil) droplets dispersed in water. In another aspect, the fine hydrocarbon droplets from such a cracker unit can comprise heavy hydrocarbons, such as tar compounds. Such emulsions can be particularly difficult to separate using conventional demulsifying agents.

[0035] Conventional demulsifying agents can comprise an alkylphenol formaldehyde resin alkoxylate, a polymeric alkoxylate, a glycol, such as a polyalkylene glycol, an organic sulfonate, a polyamine, a polyacrylate, or a combination thereof. In some aspects, a conventional demulsifying agent can comprise a polymeric alkoxylate. The use of conventional demulsifying agents can also require a significant amount of time before phase separation occurs.

[0036] In some aspects, the inventive demulsifying agent can comprise a phase transfer catalyst (PTC). A phase transfer catalyst is a compound whose addition to a two- phase system can facilitate transfer of specific moieties from one phase to another. For example, when a phase transfer catalyst is added to a two-phase organic-water system, the phase transfer catalyst can help transfer organic moieties from the water phase to the organic phase.

[0037] In another aspect, the inventive demulsifying agent can comprise a quaternary ammonium compound, a quaternary phosphonium compound, or a combination thereof. In some aspects, the inventive demulsifying agent comprises a quaternary ammonium compound. In another aspect, the inventive demulsifying agent comprises a quaternary phosphonium compound. In another aspect, the demulsifying agent comprises a quaternary ammonium salt, a quaternary phosphonium salt, or a combination thereof. In some aspects, the inventive demulsifying agent comprises a quaternary ammonium and/or quaternary phosphonium compound that can act as a phase transfer catalyst.

[0038] In another aspect, the inventive demulsifying agent can be at least partially soluble in an organic medium.

[0039] In some aspects, the inventive demulsifying agent can be represented by the general formula (I)

wherein each of Ri, R ₂ , R ₃ , and R4 are the same or different and comprise an alkyl group, an aralkyl group, or a combination thereof, wherein A comprises nitrogen or phosphorus, and wherein X comprises a counter ion.

[0040] In some aspects, the inventive demulsifying agent is represented by the compound of formula (I), wherein A is nitrogen. In another aspect, the inventive

demulsifying agent is represented by the compound of formula (I), wherein A is phosphorus. In another aspect, X comprises a halide, a propionate, a carbonate, a methosulphate, a saccharinate, an ethosulphate, a hydroxide, an acetate, a phosphate, a nitrate, or a

combination thereof. In yet another aspect, X comprises a chloride, a hydroxide, a bromide, or a combination thereof. In a specific aspect, X comprises chloride.

[0041] In various aspects, the inventive demulsifying agent can comprise a benzyltrimethyl ammonium salt, a benzyltriethyl ammonium salt, a tetrabutyl ammonium salt, a methyltrioctyl ammonium salt, or a combination thereof. Such quaternary ammonium compounds are commercially available, for example, as a 40% aqueous solution. In some aspects, the inventive demulsifying agent comprises benzyltrimethyl ammonium chloride. In another aspect, the inventive demulsifying agent comprises benzyl triethyl ammonium hydroxide. In another aspect, the inventive demulsifying agent comprises tetrabutyl ammonium chloride. In yet another aspect, the inventive demulsifying agent comprises tetrabutyl ammonium bromide. In still another aspect, the inventive demulsifying agent comprises methyltrioctyl ammonium chloride. In other aspects, the inventive demulsifying agent can comprise other quaternary ammonium and/or quaternary phosphonium salts not specifically recited herein.

[0042] The demulsifying agent can comprise a bis-quaternary ammonium and/or bis- quaternary phosphonium compound, in addition to or in lieu of a monoquaternary ammonium and/or monoquaternary phosphonium compound. In such an aspect, the bis-quaternary ammonium and/or phosphonium com ound can be represented by the general formula (II)

wherein each of Ri, R ₂ , R ₃ , R ₄ , R5, and R ₆ are the same or different and independently comprise a substituted or unsubstituted, saturated or unsaturated, branched or unbranched, cyclic or acyclic alkyl moiety and can optionally comprise one or more ether, ester, and/or amide linkages, or an aromatic or substituted aromatic group; each of Ai and A ₂ can independently comprise nitrogen and/or phosphorus; X comprises a counter ion; and Z comprises a carbon-hydrogen chain attached to each of Ai and A ₂ .

[0043] In some aspects, each of Ri to R ₆ can comprise from 1 to about 12 carbon atoms. In another aspect, X comprises a counter ion, such as an inorganic counter ion. In some aspects, the inventive demulsifying agent is represented by the compound of formula (II), wherein Ai and/or A ₂ are nitrogen. In another aspect, the inventive demulsifying agent is represented by the compound of formula (II), wherein Ai and/or A ₂ are phosphorus. In another aspect, X comprises a halide, a propionate, a carbonate, a methosulphate, a saccharinate, an ethosulphate, a hydroxide, an acetate, a phosphate, a nitrate, or a

combination thereof. In yet another aspect, X comprises a chloride, a hydroxide, a bromide, or a combination thereof. In a specific aspect, X comprises chloride. [0044] In various aspects, the inventive demulsifying agent comprises l,6-bis[l- methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethyl ammonium chloride] -hexane or triclobisonium chloride (commercially available as TRIBURON), l,10-bis(2-methyl-4- aminoquinolinium chloride)-decane (commercially available as DEQUADIN or SOROT), or CDQ prepared by the reaction of alkyl [C12, 40%, C14, 50%, C16, 10%] dimethylamine with dichloroethyl ether.

[0045] In some aspects, the inventive demulsifying agent can comprise an

epihalohydrin or a polyepihalohydrin. In another aspect, the inventive demulsifying agent does not comprise an epihalohydrin or polyepihalohydrin, or a quaternary ammonium adduct thereof. In another aspect, the inventive demulsifying agent does not comprise a quaternary organopolysiloxane or salt thereof. In still another aspect, the inventive demulsifying agent does not comprise betaine or a derivative thereof.

[0046] The inventive demulsifying agent can be contacted with an emulsion or solution to be treated as a neat component or as a solution. In various aspects, the inventive demulsifying agent can be utilized alone or in combination with one or more conventional demulsifying agents, such as, for example, a polymeric alkyloxylate. In some aspects, the inventive demulsifying agent (e.g., mono or bis quaternary ammonium and/or phosphonium compound) can be contacted with an emulsion or solution to be treated, without other conventional demulsifying agents. In another aspect, the inventive demulsifying agent can be used with one or more conventional demulsifying agents.

[0047] In some aspects, an emulsion or solution to be treated can be contacted with one or more demulsifying agents, wherein the inventive mono and/or bis quaternary ammonium and/or phosphonium compounds comprise from a trace level to about 100 % of the demulsifying agents; or from less than about 0.5 vol.% to about 100 vol.% of the demulsifying agents. In other aspects, the mono and/or bis quaternary ammonium and/or phosphonium compounds can comprise from about 5 vol.% to about 60 vol.%, for example, about 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, or 60 vol.% of the demulsifying agents; from about 5 to about 25 vol.%, for example, about 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, or 25 vol.% of the demulsifying agents; or from about 40 vol.% to about 50 vol.%, for example, about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 vol.% of the demulsifying agents. In some aspects, the mono and/or bis quaternary ammonium and/or phosphonium compounds can comprise about 50 vol.% of the

demulsifying agent, wherein the balance comprises one or more inactive solvents. In another aspect, the mono and/or bis quaternary ammonium and/or phosphonium compounds comprises from about 5 to about 25 vol.% of the demulsifying agents, wherein the balance comprises one or more inactive solvents and one or more conventional demulsifying agents, such as a polymeric alkyloxylate. In a specific aspect, an emulsion can be contacted with a solution comprising about 10 vol.% of a mono and/or bis quaternary ammonium and/or phosphonium compound, about 50 vol.% of one or more conventional demulsifying agents, such as, for example, a polymeric alkyloxylate, and about 40 vol.% of inactive solvents.

[0048] The inventive demulsifying agent can be utilized over a wide pH range as may be encountered in an olefin reactor. In some aspects, the inventive demulsifying agent can be used at a pH of about 6, for example from about 5 to about 7. In another aspect, the inventive demulsifying agent can be used at a pH of about 9, for example from about 8 to about 10.

[0049] In another aspect, the inventive demulsifying agent is stable under basic conditions, such as, for example, a pH of about 9. In yet another aspect, the inventive demulsifying agent is stable at high temperatures such as those typical in an olefin reactor. In some aspects, the inventive demulsifying agent can be used at a temperature of about 70, for example from about 60 to about 80. In another aspect, the high temperature demulsifying agent can be used at a temperature of about 100, for example from about 80 to about 120.

[0050] The inventive demulsifying agent or mixture of inventive and conventional demulsifying agents can be contacted with an emulsion or solution to be treated at a concentration of from about 10 to about 10,000 ppm, for example, about 10, 25, 50, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 7,500, or 10,000 ppm. In some aspects, the inventive demulsifying agent or mixture of inventive and conventional demulsifying agents can be contacted with an emulsion at a concentration of from about 50 to about 150 ppm, for example, about 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150 ppm.

[0051] In some aspects, the inventive demulsifying agent can provide separation of aqueous and organic phases at a concentration significantly less than conventional demulsifying agents alone. For example, a mixture comprising about 10 vol.% of a mono or bis quaternary ammonium salt, as described here, about 50 vol.% of conventional

demulsifying agents, such as, for example, polymeric alkyloxylates, and about 40 vol.% inactive solvents, when used at about 100 ppm, can provide a similar performance (i.e., time until phase separation occurs) as 1,000 ppm of conventional demulsifying agents alone.

Thus, in various aspects, the inventive composition can provide a significant improvement in resolving emulsions. In various aspects, the inventive composition can provide a similar benefit to conventional demulsifying agents along, when used at levels of from about 5 to about 20 %, for example, about 5, 6, 8, 10, 12, 14, 16, 18, or 20 % of the conventional demulsifying agents.

[0052] In various exemplary aspects, emulsions, such as, for example, gasoline and water, can be treated with a quantity of the inventive demulsifying composition. In some aspects, the inventive demulsifying composition can comprise about 50 vol.% polymeric alkoxylates and derivatives, about 40 vol.% inactive solvents, such as, for example, alcohols and aromatic solvents, and about 10 vol.% of a phase transfer catalyst. In another exemplary aspect, the inventive demulsifying composition can comprise about 50 vol.% nonylphenol- formaldehyde ethoxylate with 20 moles of ethylene oxide and 10 vol.% benzyltrimethyl ammonium chloride. In such an aspect, the solvent can comprise about 25 vol.% heavy aromatics with a balance of ethanol. In such an aspect, the formulation can be prepared by contacting the components in a stirred vessel to obtain a homogeneous or substantially homogeneous composition.

[0053] The present invention can be described in a various aspects, as recited herein and described below.

[0054] Aspect 1 : The present invention provides a method for at least partially demulsifying an emulsion, the method comprising contacting the emulsion with a

composition comprising a monoquaternary ammonium salt, monoquaternary phosphonium salt, a bis-quaternary ammonium salt, a bis-quaternary phosphonium salt, or a combination thereof; wherein the mono-quaternary salt, if present, is represented by a general formula

R ₂

x - A ⁺ - R ₄ X- wherein each of Ri R ₂ R _3i and R4 are same or different and comprises an alkyl group, an aralkyl group, or a combination thereof, wherein A comprises nitrogen or phosphorus, and wherein X can comprise any ionic counter anion; wherein the bis-quaternary ammonium salt, if present, is represented by a general formula

wherein each of Ri-R ₆ are the same or different and independently comprise from 1 to 12 carbons, an alkyl group, an aralkyl group, or a combination thereof; wherein each of Ai and A ₂ independently comprise nitrogen or phosphorus; wherein Z comprises a carbon-hydrogen chain, and wherein X comprises a counter anion.

[0055] Aspect 2: The method of aspect 1, wherein the composition comprises a phase transfer catalyst.

[0056] Aspect 3: The method of aspect 1 or 2 , wherein the composition comprises a monoquaternary ammonium salt.

[0057] Aspect 4: The method of any one or more of aspects 1 to 3, wherein the composition comprises a bis-quaternary ammonium salt.

[0058] Aspect 5: The method of any one or more of aspects 1 to 4, wherein the composition further comprises one or more conventional demulsifiers.

[0059] Aspect 6: The method of aspect 5, wherein the one or more conventional demulsifiers comprise about 50 wt.% of an active ingredient and about 50 wt.% of an inactive solvent.

[0060] Aspect 7: The method of aspect 6, wherein the active ingredient comprises a polymeric alkoxylate, a glycol, an organic sulfonate, a polyamine, a polyacrylate, or a combination thereof.

[0061] Aspect 8: The method of aspect 6, wherein the inactive solvent comprises an alcohol, an aromatic hydrocarbon, or a combination thereof.

[0062] Aspect 9: The method of any one or more of aspects 1 to 8, wherein the composition comprises from less than about 0.5 vol.% to about 100 vol.% of the

monoquaternary ammonium salt, the bis-quaternary ammonium salt, or the combination thereof.

[0063] Aspect 10: The method of any one or more of aspects 1 to 9, wherein the emulsion comprises a hydrocarbon and water.

[0064] Aspect 11: The method of any one or more of aspects 1 to 10, wherein the emulsion comprises gasoline and water. [0065] Aspect 12: The method of any one or more of aspects 1 to 11, wherein the emulsion comprises a plurality of oil droplets dispersed in water.

[0066] Aspect 13: The method of aspect 12, wherein the plurality of oil droplets comprise polynuclear aromatic hydrocarbons.

[0067] Aspect 14: The method of any one or more of aspects 1 to 12, wherein the emulsion comprises a water phase containing no or substantially no water bubbles with organic membranes.

[0068] Aspect 15: The method of any one or more of aspects 1 to 14, wherein the composition is contacted with the emulsion in an amount ranging from about 50 ppm to about 150 ppm.

[0069] Aspect 16: The method of any one or more of aspects 1 to 15, wherein the monoquaternary ammonium salt comprises a benzyltrimethyl ammonium salt, a

benzyltriethyl ammonium salt, a tetrabutyl ammonium salt, a methyltrioctyl ammonium salt, or a combination thereof.

[0070] Aspect 17: The method of any one or more of aspects 1 to 16, wherein the bis- quaternary ammonium salt comprises 1, 6-bis[l-methyl-3-(2,2,6-trimethylcyclohexyl)- propyldimethyl ammonium chloride] -hexane; triclobisonium chloride; 1, 10-bis(2-methyl-4- aminoquinolinium chloride)-decane; CDQ prepared by reaction of alkyl [C12, 40%, C14, 50%; C16, 10%] dimethylamine with dichloroethyl ether; or a combination thereof.

[0071] Aspect 18: The method of any one or more of aspects 1 to 17, wherein the composition comprises at least one monoquaternary ammonium salt and at least one bis- quaternary ammonium salt.

[0072] Aspect 19: The method of any one or more of aspects 1 to 18, wherein X comprises a chloride, a hydroxide, a bromide, or a combination thereof.

[0073] Aspect 20: The method of any one or more of aspects 1 to 19, wherein X comprises a halide, a propionate, a carbonate, a methosulphate, a saccharinate, an

ethosulphate, a hydroxide, an acetate, a phosphate, a nitrate, or a combination thereof.

[0074] Aspect 21: The method of any one or more of aspects 1 to 20, wherein X comprise chloride.

[0075] Aspect 22: The method of any one or more of aspects 1 to 4 or 6 to 21, wherein no conventional demulsifier is contacted with the emulsion or the composition.

Aspect 23. The method of any one or more of aspects 1 to 22, wherein, when present, the monoquaternary ammonium salt comprises a benzyltrimethyl ammonium salt, a benzyltriethyl ammonium salt, a tetrabutyl ammonium salt, a methyltrioctyl ammonium salt, or a combination thereof; and/or the bis-quaternary ammonium salt comprises l,6-bis[l- methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethyl ammonium chloride] -hexane;

triclobisonium chloride; l,10-bis(2-methyl-4-aminoquinolinium chloride)-decane; CDQ prepared by reaction of alkyl [C12, 40%, C14, 50%; C16, 10%] dimethylamine with dichloroethyl ether; or a combination thereof.

EXAMPLES

[0076] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.

[0077] In a first example, emulsions of water and gasoline were prepared and treated with various demulsifying chemicals. Water and gasoline samples were collected from a commercial olefins production facility. Water (i.e., process water) samples were obtained between a settling tank and the Dispersed Oil Extraction (DOX) unit. Gasoline samples were obtained from the last compartment of a quench water settling tank.

[0078] Testing was performed at room temperature using 200 ml of gasoline and 200 ml of process water. The gasoline and water samples were added to a three-neck 500 ml flask with a TEFLON-coated magnetic stirrer. The gasoline and water mixture was maintained at 20 °C and stirred at a rate such that the contents did not splash out of the flask. The demulsifying agent was then added to the flask using a syringe. After a period of two hours (i.e., after addition of the demulsifying agent), stirring was stopped and a stop-watch was started. The time at which the water and oil layers separated was then recorded.

[0079] Initially, conventional demulsifying agents were used. The demulsifying agents were added in concentrations ranging from about 50 ppm to about 1,000 ppm, and at a pH of from about 6 to about 9. Table 1, below, shows the results obtained when using a conventional demulsifying agent comprising about 50 vol.% active ingredients (polymeric alkoxylates and derivatives) and about 50 vol.% inactive solvent (alcohol and aromatic hydrocarbon). Table 1. Conventional Demulsifying Agent

[0080] Emulsions of gasoline and water were prepared and treated with the inventive demulsifying composition comprising about 50 vol.% polymeric alkoxylates and derivatives, about 40 vol.% inactive solvents, such as, for example, alcohols and aromatic solvents, and about 10 vol.% of a phase transfer catalyst. In some aspects, an exemplary formulation comprises 50 vol.% nonylphenol-formaldehyde ethoxylate with 20 moles of ethylene oxide and 10 vol.% benzyltrimethyl ammonium chloride. In such an aspect, the solvent used comprises 25 vol.% heavy aromatics with a balance of ethanol. In such an aspect, the formulation is prepared by mixing the components in a stirred vessel to obtain a

homogeneous or substantially homogeneous composition. Table 2, below, illustrates the results obtained when using the inventive demulsifying agent.

Table 2. Inventive Demulsifying Agent

[0081] As illustrated in Tables 1 and 2, the inventive demulsifying agent provided separation of water and gasoline layers in significantly less time and at lower concentrations than the conventional demulsifying agents. In some aspects, use of 100 ppm of the inventive emulsifying agent was approximately equivalent to 1,000 ppm of the conventional emulsifying agent. [0082] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited.

[0083] It is to be understood that the present compounds, compositions, articles, systems, devices, and/or methods are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials have been described herein.

[0084] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.