Nanobubble containing compositions and methods of use

Abstract

A nanobubble containing composition is disclosed that includes a plurality of gas-filled nanobubbles and a nanobubble stabilizer. The nanobubble containing composition can contain a continuous phase and a discontinuous phase dispersed in the continuous phase. Methods of using the nanobubble containing composition are also disclosed.

Description

NANOBUBBLE CONTAINING COMPOSITIONS AND METHODS OF USE CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to US Provisional application 63 / 653,128, filed May 29, 2024. The contents of the referenced application are incorporated into the present application by reference. BACKGROUND OF THE INVENTION A. Field of the Invention

[0002] The invention generally concerns nanobubble containing compositions and methods of using nanobubble containing compositions. The invention is more particularly directed to nanobubble containing compositions that can include a continuous phase, a discontinuous phase comprising gas-filled nanobubbles, and a nanobubble stabilizer. The discontinuous phase can be dispersed in the continuous phase, and the nanobubble containing compositions can be formulated such that the gas-filled nanobubbles remain dispersed in the continuous phase. The invention is also directed to various methods of using such nanobubble containing compositions. B. Description of Related Art

[0003] There have been attempts to utilize gas-liquid mixture fluids containing fine bubbles in various industries and fields of applications. To illustrate, fine bubbles with diameters in the nanometer-sized range (sometimes referred to simply as “nanobubbles”) may have a variety of interesting properties. For example, nanobubbles can have properties, such as: neutral buoyancy; hydrophobicity; water surface tension reduction capabilities; oxidative properties; negative zeta potential; a hard surface that makes such bubbles act more like particles; and / or various combinations thereof. One exemplary drawback of nanobubbles is their stability, as nanobubbles tend to coalesce more quickly than desired, thereby limiting their potential usage. SUMMARY OF THE INVENTION

[0004] A discovery has been made that provides a solution to at least one or more of the aforementioned problems associated with nanobubbles. In one aspect, it has been discovered that utilization of a nanobubble stabilizer in a nanobubble containing composition may provide numerous advantages. For example, a nanobubble stabilizer may advantageously increase the concentration of nanobubbles in a nanobubble containing composition. As another example, a nanobubble stabilizer may advantageously reduce or eliminate coalescence of298150774.1 - 1 - CHPX.P0002WO / 1001347562nanobubbles in a nanobubble containing composition, such that a satisfactory concentration of nanobubbles remains available to a process. In another aspect, it has been discovered that such a reduced tendency towards rapid coalescence of the nanobubbles has the associated advantage of broadening the potential applications in which formulations including such stabilized nanobubbles may be utilized.

[0005] In a particular aspect, it has been discovered that formulations (the terms composition and formulation can be used interchangeably throughout this specification) including the stabilized nanobubbles of the present disclosure may enhance the performance of various oilfield chemistries. In one aspect, such formulations may increase the performance of various oilfield surfactants, thereby providing for enhanced (e.g., faster) oil recovery. In another aspect, such formulations may increase the effectiveness of various corrosion inhibitors by increasing water partitioning of oil soluble products. In some aspects, formulations including the stabilized nanobubbles of the present disclosure may enhance the performance of a variety of other production chemicals, such as corrosion inhibitors, asphaltene inhibitors, emulsion breakers, paraffin inhibitors, scale inhibitors, H2S scavengers, polymeric solutions, and fracking fluids. In some particular, aspects, the nanobubble stabilizer can include any one of, any combination of, or all of benzalkonium chloride, lauryl hydroxysultaine, lauryl sultaine, and / or Surfonic L12-3 (CAS # 66455-15-0). In some particular embodiments, the nanobubble stabilizer can include lauryl hydroxysultaine or lauryl sultaine or both in combination with Surfonic L12-3 (CAS # 66455-15-0).

[0006] In some aspects, formulations including the stabilized nanobubbles of the present disclosure may be utilized in a variety of other applications, such as: gas lift; microbiological control; reverse emulsion breaking / phase separation; water clarification; and cleaning applications (e.g., pipelines, biofilms, reverse osmosis membranes, etc.). Numerous other advantages associated with the present invention are described herein.

[0007] In one aspect of the present invention, a nanobubble containing composition is disclosed that includes an aqueous continuous phase, a discontinuous phase, and a nanobubble stabilizer. The discontinuous phase can include a plurality of gas-filled nanobubbles. The discontinuous phase is dispersed in the aqueous continuous phase, and the gas-filled nanobubbles remain dispersed in the aqueous continuous phase, such as when the aqueous continuous phase has a total dissolved solids of at least 100 parts per million (ppm).

[0008] In one aspect of the present invention there is disclosed a nanobubble containing composition that includes a non-aqueous continuous phase, a discontinuous phase, and a nanobubble stabilizer. The discontinuous phase can include a plurality of gas-filled298150774.1 - 2 - CHPX.P0002WO / 1001347562nanobubbles. The discontinuous phase is dispersed in the non-aqueous continuous phase, and the gas-filled nanobubbles remain dispersed in the non-aqueous continuous phase.

[0009] In another aspect of the present invention, there is disclosed a nanobubble containing composition that includes an emulsion comprising an aqueous phase and a non- aqueous phase. The nanobubble containing composition includes a plurality of gas-filled nanobubbles and at least one surfactant that causes the gas-filled nanobubbles to remain dispersed in the emulsion.

[0010] In yet another aspect of the present invention, a method of contacting one of the aforementioned nanobubble containing compositions with a second composition. In some aspects, the second composition can include hydrocarbons (e.g., that are comprised in a subterranean formation). In other aspects, the second compositions can include production chemicals such as corrosion inhibitors, asphaltene inhibitors, emulsion breakers, paraffin inhibitors, scale inhibitors, H2S scavengers, water clarifiers, and fracking fluids.

[0011] Also disclosed in the context of the present invention are aspects 1-28. Aspect 1 is a nanobubble containing composition comprising: an aqueous continuous phase; a discontinuous phase comprising a plurality of gas-filled nanobubbles; and a nanobubble stabilizer, wherein the discontinuous phase is dispersed in the aqueous continuous phase, and wherein the gas-filled nanobubbles remain dispersed in the aqueous continuous phase. Aspect 2 is the nanobubble containing composition of aspect 1, wherein the aqueous continuous phase has a total dissolved solids level of at least 100 parts per million (ppm).

[0012] Aspect 3 is a nanobubble containing composition comprising: a non-aqueous continuous phase; a discontinuous phase comprising a plurality of gas-filled nanobubbles; and a nanobubble stabilizer, wherein the discontinuous phase is dispersed in the non-aqueous continuous phase, and wherein the gas-filled nanobubbles remain dispersed in the non-aqueous continuous phase.

[0013] Aspect 4 is a nanobubble containing composition comprising: an emulsion comprising an aqueous phase and a non-aqueous phase; a plurality of gas-filled nanobubbles; and at least one surfactant that causes the gas-filled nanobubbles to remain dispersed in the emulsion.

[0014] Aspect 5 is a method comprising: contacting the nanobubble containing composition of any one of claims 1 to 4 with a second composition. Aspect 6 is the method of aspect 5, wherein the second composition comprises hydrocarbons. Aspect 7 is the method of aspect 6, wherein the hydrocarbons are comprised in a subterranean formation. Aspect 8 is the method of aspect 7, wherein the method includes contacting the nanobubble containing298150774.1 - 3 - CHPX.P0002WO / 1001347562composition of aspect 1 with the hydrocarbons such that the gas-filled nanobubbles enter into an interstitial space defined between the hydrocarbons and the subterranean formation to reduce interfacial tension between the hydrocarbons and the subterranean formation. Aspect 9 is the method of aspect 8, wherein the nanobubble stabilizer of the nanobubble containing composition of aspect 1 includes an oil recovery composition comprising a blend of an amphoteric surfactant and a non-ionic surfactant. Aspect 10 is the method of aspect 9, wherein contacting the nanobubble containing composition of aspect 1 with the hydrocarbons results in enhanced oil recovery from the subterranean formation. Aspect 11 is the method of aspect 10, wherein the enhanced oil recovery from the subterranean formation corresponds to a faster rate of oil recovery relative to the oil recovery composition comprising the blend of the amphoteric surfactant and the non-ionic surfactant. Aspect 12 is the method of aspect 6, wherein the hydrocarbons are comprised in produced oil, liquid condensate, or a combination thereof. Aspect 13 is the method of aspect 5, wherein the second composition comprises water in a subterranean formation or in a production fluid. Aspect 14 is the method of aspect 5, wherein the second composition is associated with a hydrogen system, a carbon dioxide system, an upstream system, a downstream system, a mixed upstream / downstream system, or any combination thereof. Aspect 15 is the method of aspect 5, wherein the second composition comprises one or more production chemicals. Aspect 16 is the method of aspect 5, wherein the second composition comprises polymer. Aspect 17 is the nanobubble containing composition of any one of aspects 1 to 4, wherein the nanobubble stabilizer includes one or more materials that adsorb onto a surface of individual gas-filled nanobubbles of the plurality of gas-filled nanobubbles. Aspect 18 is the nanobubble containing composition of any one of aspects 1 to 4, wherein the nanobubble stabilizer includes one or more materials that attach onto a surface of individual gas-filled nanobubbles of the plurality of gas-filled nanobubbles. Aspect 19 is the nanobubble containing composition of aspect 1, wherein the nanobubble stabilizer comprises at least one of an amphoteric surfactant and a non-ionic surfactant. Aspect 20 is the nanobubble containing composition of aspect 19, wherein the nanobubble stabilizer includes a blend of the amphoteric surfactant and the non-ionic surfactant. Aspect 21 is the nanobubble containing composition of aspect 20, wherein an oil recovery composition includes the blend, and wherein the blend further comprises one or more demulsifiers. Aspect 22 is the nanobubble containing composition of any one of aspects 1 to 4, wherein the nanobubble stabilizer comprises a cationic surfactant. Aspect 23 is the nanobubble containing composition of aspect 22, wherein the cationic surfactant is benzalkonium chloride. Aspect 24 is the nanobubble containing composition of aspect 22, wherein a corrosion inhibition composition298150774.1 - 4 - CHPX.P0002WO / 1001347562includes the cationic surfactant, and wherein the corrosion inhibition composition further comprises a corrosion inhibitor. Aspect 25 is the method of aspect 5, wherein the second composition comprises an asphaltene inhibitor, and wherein the method includes contacting the nanobubble containing composition of aspect 3 with the asphaltene inhibitor. Aspect 26 is the method of aspect 25, wherein a combination of the nanobubble containing composition of aspect 3 and the asphaltene inhibitor results in a reduced asphaltene deposition rate relative to a composition that includes the asphaltene inhibitor but does not include the gas-filled nanobubbles. Aspect 27 is the method of aspect 26, wherein the second composition comprises an emulsion breaking material, and wherein the method includes contacting the nanobubble containing composition of aspect 3 with the emulsion breaking material. Aspect 28 is the method of aspect 27, wherein a combination of the nanobubble containing composition of aspect 3 and the emulsion breaking material results in a faster water drop and sharper interface relative to a composition that includes the emulsion breaking material but does not include the gas-filled nanobubbles.

[0015] Other embodiments of the invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention applies to other aspects of the invention as well and vice versa. Each embodiment described herein is understood to be embodiments of the invention that are applicable to other aspects of the invention. It is contemplated that any embodiment or aspect discussed herein can be combined with other embodiments or aspects discussed herein and / or implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0016] The following includes definitions of various terms and phrases used throughout this specification.

[0017] The term “nanobubble” includes without limitation any of various gas bubbles in the nanometer-size range (e.g., ranging from 1 nm to 1000 nm in diameter), according to different aspects of the present disclosure.

[0018] The term “nanobubble stabilizer” includes without limitation any of various types of materials that can stabilize the nanobubbles in a composition. This stabilizing can occur by the nanobubble stabilizer adsorbing onto a surface of the nanobubble. In certain aspects, the adsorption can be the nanobubble stabilizer attaching to a surface of the nanobubble. The attachment can be through an ionic bond, a covalent bond, a hydrogen bond, a Van der Walls interaction, or hydrophobic interactions between the stabilizer and the surface of the nanobubble.298150774.1 - 5 - CHPX.P0002WO / 1001347562

[0019] The term “functional ingredient” includes without limitation any of various types of additional materials that can be included in the nanobubble containing compositions. The functional ingredients may provide desired properties and functionalities to the nanobubble containing compositions.

[0020] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0021] The terms “wt.%”, “vol.%”, or “mol.%” refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, which includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0022] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and / or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0023] The term “effective,” as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0024] The use of the words “a” or “an” when used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having” in the claims, or the specification, may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0025] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0026] The nanobubble containing compositions of the present invention can “comprise,” “consist essentially of,” or “consist of” particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phrase “consisting essentially of,” in one non-limiting aspect, a basic and novel characteristic of the nanobubble containing compositions of the present invention is that the presence of a nanobubble stabilizer may result in a reduced tendency towards rapid coalescence of298150774.1 - 6 - CHPX.P0002WO / 1001347562nanobubbles in the compositions, such that a satisfactory concentration of nanobubbles remains available for a given process / application.

[0027] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0029] FIG. 1 is an illustration of comparative experimental testing data associated with the effects of nanobubbles on oil recovery percentage over time, according to some aspects of the present invention.

[0030] FIG. 2 is an illustration of comparative experimental testing data associated with the effects of nanobubbles imparted by the expansion-contraction method and nanobubbles imparted by the sonic probe method on corrosion rate and protection percentage, according to some aspects of the present invention.

[0031] FIG. 3 is an illustration of comparative experimental testing data associated with the effects of nanobubbles imparted by the expansion-contraction method and nanobubbles imparted by the sonic probe method on corrosion rate and protection percentage, according to some aspects of the present invention.

[0032] FIG. 4 is an illustration of comparative experimental testing data associated with the effects of nanobubbles imparted by the expansion-contraction method and nanobubbles imparted by the sonic probe method on corrosion rate and protection percentage, according to some aspects of the present invention.

[0033] FIG. 5 is an illustration of comparative experimental testing data associated with the effects of nanobubbles imparted by the expansion-contraction method and298150774.1 - 7 - CHPX.P0002WO / 1001347562nanobubbles imparted by the sonic probe method on corrosion rate and protection percentage, according to some aspects of the present invention.

[0034] FIG. 6 is an illustration of comparative experimental testing data associated with the effects of nanobubbles imparted by the expansion-contraction method and nanobubbles imparted by the sonic probe method on corrosion rate and protection percentage, according to some aspects of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0035] The present disclosure describes nanobubble containing compositions and methods of use of such nanobubble containing compositions. In one aspect, the present disclosure is directed to the use of a nanobubble stabilizer (e.g., surfactants, etc.) to stabilize nanobubbles in an aqueous solution (representing one type of nanobubble containing composition). In another aspect, the present disclosure is directed to the use of a nanobubble stabilizer to stabilize nanobubbles in a non-aqueous solution (representing another type of nanobubble containing composition). In yet another aspect, the present disclosure is directed to the use of such nanobubble containing compositions to enhance the performance of various oilfield chemistries. In a particular aspect, the nanobubble containing compositions of the present disclosure may be utilized for an enhanced oil recovery (EOR) application (representing one type of “downhole” oilfield chemistry application). In various aspects, the nanobubble containing compositions of the present disclosure may be utilized for numerous types of other downhole oilfield chemistry applications. Alternatively, in various aspects, the nanobubble containing compositions of the present disclosure may be utilized for other types of applications (e.g., “top-side” applications, such as top-side oilfield chemistry applications, among numerous other alternatives as described further herein).

[0036] As described further herein, combining nanobubbles with surfactant-based chemistries may provide various advantages when utilized with various oilfield chemistries to improve / enhance their performance. To illustrate, combining nanobubbles with surfactant- based chemistries can increase the concentration of nanobubbles created and / or increase the stability of the nanobubbles, reducing or potentially eliminating coalescence, such that a sufficient concentration of the nanobubbles is available for a given process / application. As one illustrative, non-limiting example, the stabilized nanobubbles of the present disclosure may be utilized for enhanced oil recovery (in one particular use case, as described further herein). As another illustrative, non-limiting example, the stabilized nanobubbles of the present disclosure298150774.1 - 8 - CHPX.P0002WO / 1001347562may be utilized for increased effectiveness of certain corrosion inhibitors by increasing water partitioning of oil soluble products (in another particular use case, as described further herein).

[0037] Nanobubbles can have interesting properties, such as being neutrally buoyant, being hydrophobic, having the ability to lower the surface tension of water, being oxidative, and / or can have negative zeta potential and a surface that makes them act more like particles. These interesting properties are of particular interest for various oilfield chemistries, since these properties could be leveraged to enhance the performance of various oilfield chemistry products. Unfortunately, the inventors of the present application have found that generation of nanobubbles in the laboratory has been challenging. As explained in the Examples, the inventors have evaluated a commercially available product whose nanobubble generator is primarily utilized in agriculture and aquaculture industries. The inventors have found that the commercially available equipment did not generate the number of nanobubbles expected. Further, the inventors have found that the nanobubbles that were generated using this equipment tended to coalesce in a matter of hours. Such quick coalescence is particularly undesirable in oilfield chemistry applications, as it is impractical and cost prohibitive for such a nanobubble generator to be placed at every well or at every site where such nanobubbles may be advantageous. Accordingly, the nanobubble containing compositions of the present disclosure (that include a nanobubble stabilizer) are particularly advantageous, as the nanobubbles within such compositions can be stable and / or may be added to various formulations (e.g., oilfield chemistry formulations, etc.) and then shipped out to customer sites for implementation.

[0038] Further, the nanobubble containing compositions of the present invention may also be used in a variety of other processes / applications. As illustrative, non-limiting examples, the nanobubble containing compositions of the present invention may be advantageous when utilized in one or more the following processes / applications: wastewater treatment; wastewater and sewer management; water treatment; food sanitation; carpet cleaning; building cleaning; cloth and textile cleaning; dry cleaning; fur cleaning; jewelry cleaning; leather cleaning; carpet cleaning; window cleaning; pool cleaning; motor vehicle (car, truck, bus, bicycle, motorcycle, etc.) cleaning; train cleaning; ship cleaning; aircraft cleaning; oil and gas well treatment; oil refining; fuel treatment; and steam assisted gravity drainage.

[0039] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.298150774.1 - 9 - CHPX.P0002WO / 1001347562A. Nanobubble Containing Composition (Aqueous Continuous Phase) 1. Aqueous Continuous Phase

[0040] A nanobubble containing composition can include an aqueous continuous phase. In some aspects, the aqueous continuous phase can have a total dissolved solids level of at least 100 ppm. In some aspects, the aqueous continuous phase can have a relatively high salinity (e.g., a salinity of at least 100 ppm, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 ppm or more or any range or number therein). It has been found that the gas-filled nanobubbles of the present disclosure remain dispersed in the aqueous continuous phase when the nanobubble containing composition has a salinity of at least 100 ppm, despite the relatively high salinity. 2. Discontinuous Phase

[0041] The nanobubble containing composition can include a discontinuous phase comprising a plurality of gas-filled nanobubbles. In some aspects, such nanobubbles can have an average diameter 1 nm to up to 1000 nm or any range or number therein (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 960, 970, 980, 990, 991, 992, 993, 994, 995, 996, 997, 998, or 999 nm). In some preferred aspects, the nanobubbles have an average size of 20 nm to 500 nm. The discontinuous phase is dispersed in the aqueous continuous phase. 3. Nanobubble Stabilizer

[0042] The nanobubble containing composition can include a nanobubble stabilizer. In some aspects, the nanobubble containing composition can include a nanobubble stabilizer, such as 1 parts per million (ppm) to 500,000 ppm or any range or number therein (e.g., 2, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 5000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 46,000, 47,000, 48,000, 49,000, 49,500, 49,900, 50,000, 55,000, 60,000, 70,000, 80,000, 90,000, 100,000, 110,000, 120,000, 130,000, 140,000, 150,000, 160,000, 170,000, 180,000, 190,000, 200,000, 210,000, 220,000, 230,000, 240,000, 250,000, 260,000, 270,000, 280,000, 290,000, 300,000, 310,000, 320,000, 330,000, 340,000, 350,000, 360,000, 370,000, 380,000, 390,000, 400,000, 410,000, 420,000, 430,000, 440,000, 450,000, 460,000, 470,000, 480,000, 490,000, or 500,000 ppm) of the nanobubble stabilizer. The nanobubble stabilizer can include without limitation any of various types of materials that can stabilize the nanobubbles in a composition. This stabilizing can occur by the nanobubble stabilizer adsorbing onto a surface of the nanobubble. In certain aspects, the298150774.1 - 10 - CHPX.P0002WO / 1001347562adsorption can be the nanobubble stabilizer attaching to a surface of the nanobubble. The attachment can be through an ionic bond, a covalent bond, a hydrogen bond, a Van der Walls interaction, or hydrophobic interactions between the stabilizer and the surface of the nanobubble.

[0043] In some aspects, the nanobubble stabilizer can include one or more amphoteric (also referred to as “zwitterionic”) surfactants, one or more non-ionic surfactants, one or more cationic surfactants, one or more anionic surfactants, or any combinations thereof. In a particular aspect, the nanobubble stabilizer can include a blend of an amphoteric surfactant and a non-ionic surfactant. As described further herein with respect to EXAMPLE 1, a nanobubble containing composition including such a blend may be particularly useful for an enhanced oil recovery (EOR) application, such as for recovery of hydrocarbons from a subterranean formation. In such an EOR application, the stabilized nanobubbles of the nanobubble containing composition may enter into an interstitial space defined between the hydrocarbons and the subterranean formation to reduce interfacial tension between the hydrocarbons and the subterranean formation. In some particular embodiments, the nanobubble stabilizer can include a blend of lauryl hydroxysultaine or lauryl sultaine or both in combination with Surfonic L12-3 (CAS # 66455-15-0).

[0044] Non-limiting examples of amphoteric surfactants that can be used in the context of the present invention include betaines, sultaines, alkylamphoacetates, amphodiacetates, alkylamphopropionates, alkyliminodipropionates, amphodipropionates or any combination thereof. Examples of betain include an alkyl betaine, an alkylamido betaine, or a sulfobetaine. The alkyl betaine can comprise an alkyl dimethyl betaine. The alkylamidobetaine can comprise an alkylamido propyl betain such as cocoamido propyl betaine, a capryloamidopropyl betaine, or a caprylamidopropyl betaine. The sulfobetaine can comprise N-decyl-N,N-dimethyl-3- ammonio-1-propanesulfonate or dimethyl-(2-hydroxyethyl)-(3-sulfopropyl) ammonium. A suitable sultane can comprise lauryl hydroxysultaine, lauryl sultaine, or an alkylamidopropyl hydroxysultane such as lauramidopropyl hydroxysultaine. A suitable amphodiacetate can comprise an alkylamphoacetate.

[0045] Non-limiting examples of non-ionic surfactants that can be used in the context of the present invention include Surfonic L12-3 (CAS # 66455-15-0), an alkoxylate, an amine oxide, a sorbitan ester, a carboxylic compound, a polyalkoxylated glyceride or any combination thereof. For example, the alkoxylate can comprise an alkoxylated alcohol or ether, an alkylphenol alkoxylate, or an alkyl ethoxylate. The amine oxide can comprise an alkyl dimethyl amine oxide, an alkyl-bis (2-hydroxyethyl) amine oxide, an alkyl amidopropyl298150774.1 - 11 - CHPX.P0002WO / 1001347562dimethyl amine oxide, or an alkylamidopropyl-bis(2-hydroxyethyl) amine oxide. The sorbitan ester can comprise a polyalkoxylated sorbitan ester. The carboxylic compound can comprise a carboxylic acid or a carboxylic ether.

[0046] Non-limiting examples of cationic surfactants that can be used in the context of the present invention include a quaternary amine or a quaternary ammonium salt thereof or any combination thereof. The quaternary amine can comprise a monoalkyl quaternary amine. For example, the monoalkyl quaternary amine can comprise cocotrimonium chloride, soyatrimonium chloride, stearyltrimonium chloride, and / or behentrimonium chloride. The quaternary amine can include a dialkyl quaternary amine such as a dialkly dimethyl quaternium ammonium salt. For example, the dialkyl dimethyl quaternium ammonium salt can include dicetyldimethyl ammonium chloride, dicocodimethyl ammonium chloride, or distearyldimethyl ammonium chloride. The quaternary ammonium salt can include benzalkonium chloride, benzethonium chloride, cetrimonium chloride, or dodecyl dimethyl ammonium chloride, cetylpyridinium chloride, tetraethylammonium bromide, behentrimonium methosulfate, behentrimonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethylbenzyl ammonium chloride, dodecyl dimethyl ammonium chloride, dioctyldimethylammonium chloride, or cetyltrimethylammonium bromide.

[0047] Non-limiting examples of anionic surfactants that can be used in the context of the present invention include an alkyl carboxylate, an alkyl sarcosinate, an alkyl sulfosuccinate, a sulfosuccinamate, an alkyl phosphate, an alkyl sulfonate, an alkyl sulfate or any combination thereof. For example, the alkyl carboxylate can comprise a fatty carboxylate or an alkyl ether carboxylate; the alkyl sulfosuccinate can comprise a monoalkylsulfosuccinate or dialkylsulfosuccinate; the alkyl phosphate can comprise an alkyl phosphate ester or an ethoxylated alkyl phosphate ester; the alkyl sulfonate can comprise an alkyl aryl sulfonate, an ester sulfonate (eg., a C12-C18 ester sulfonate), an olefin sulfanate (eg., a C14-C24 alpha olefin sulfonate or a C15-C17 internal olefin sulfonate), or a paraffin sulfonate; the alkyl sulfate can comprise an alcohol sulfate or an alcohol ether sulfate (eg., a C13-C18 alcohol ether sulfate). 4. Functional Ingredient(s)

[0048] In various embodiments, the nanobubble containing composition can (optionally) include one or more additional functional ingredients. The functional ingredients can provide desired properties and functionalities to the nanobubble containing composition.

[0049] In some embodiments, the nanobubble containing composition may include additional corrosion inhibitors, surfactants, polymers, pH modifiers, surfactants, hydrate298150774.1 - 12 - CHPX.P0002WO / 1001347562inhibitors, scale inhibitors, biocides, salt substitutes, relative permeability modifiers, sulfide scavengers, breakers, asphaltene inhibitors, paraffin inhibitors, metal complexing agents (chelants), emulsifiers or coupling agents, demulsifiers, iron control agents, friction reducers, drag reducing agents, flow improvers, viscosity reducers, stability component, and the like. Exemplary types of the various additional functional ingredients is included in U.S. Patent No. 11,242,480, which is incorporated by reference in its disclosure of the various listings of additional functional ingredients.

[0050] In further embodiments, the nanobubble containing composition may include at least one additional component selected from the group consisting of additional corrosion inhibitors, pH modifiers, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, metal complexing agents (chelants), surfactants, emulsifiers or coupling agents, water clarifiers, dispersants, emulsion breakers and combinations thereof.

[0051] According to embodiments of the disclosure, the various additional functional ingredients may be provided in the nanobubble containing composition in an amount from about 0 wt. % and about 40 wt. %, from about 0 wt. % and about 30 wt. %, from about 0 wt. % and about 20 wt. %, from about 0.01 wt. % and about 40 wt. %, from about 0.1 wt. % and about 40 wt. %, from about 0.1 wt. % and about 30 wt. %, from about 0.1 wt. % and about 20 wt. %, or from about 1 wt. % and about 2 wt. %, or from about 1 wt. % and about 10 wt. %. In some aspects, the nanobubble containing composition can include 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %, or any range or number therein, based on the total weight of the composition, of a functional ingredient or combination of functional ingredients. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range. Additional examples of additional functional ingredients are listed herein as exemplary wt. % ranges based on the total weight of the nanobubble containing composition, in addition these weight percentage ranges.

[0052] The nanobubble containing composition can optionally include an organic sulfur compound, such as a mercaptoalkyl alcohol, mercaptoacetic acid, thioglycolic acid, 3,3′- dithiodipropionic acid, thiosulfate, thiourea, L-cysteine, or tert-butyl mercaptan. An exemplary mercaptoalkyl alcohol comprises 2-mercaptoethanol. The organic sulfur compound can be included in the nanobubble containing compositions from about 0 to about 15 wt. % or any range or number therein (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 wt. %) of the composition.298150774.1 - 13 - CHPX.P0002WO / 1001347562

[0053] The nanobubble containing composition can optionally include a demulsifier. An exemplary demulsifier comprises an oxyalkylate polymer, such as a polyalkylene glycol. The demulsifier can be included in the nanobubble containing composition from about 0 to 50 wt. % or any range or number therein (e.g., 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %) of the composition, based on total weight of the composition.

[0054] The nanobubble containing composition can optionally include an asphaltene inhibitor. Suitable asphaltene inhibitors include, but are not limited to, aliphatic sulfonic acids; alkyl aryl sulfonic acids; aryl sulfonates; lignosulfonates; alkylphenol / aldehyde resins and similar sulfonated resins; polyolefin esters; polyolefin imides; polyolefin esters with alkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefin amides; polyolefin amides with alkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefin imides with alkyl, alkylenephenyl or alkylenepyridyl functional groups; alkenyl / vinyl pyrrolidone copolymers; graft polymers of polyolefins with maleic anhydride or vinyl imidazole; hyperbranched polyester amides; polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkyl succinates, sorbitan monooleate, and polyisobutylene succinic anhydride. The asphaltene inhibitor can be included in the compositions from about 0.1 to 50 wt.% or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %) of the composition, based on total weight of the composition.

[0055] The nanobubble containing composition can optionally include a paraffin inhibitor. Suitable paraffin inhibitors include, but are not limited to, paraffin crystal modifiers, and dispersant / crystal modifier combinations. Suitable paraffin crystal modifiers include, but are not limited to, alkyl acrylate copolymers, alkyl acrylate vinylpyridine copolymers, ethylene vinyl acetate copolymers, maleic anhydride ester copolymers, branched polyethylenes, naphthalene, anthracene, microcrystalline wax and / or asphaltenes. Suitable dispersants include, but are not limited to, dodecyl benzene sulfonate, oxyalkylated alkylphenols, and oxyalkylated alkylphenolic resins. The paraffin inhibitor can be included in the nanobubble containing compositions from about 0.1 to 50 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %) of the composition, based on total weight of the composition.298150774.1 - 14 - CHPX.P0002WO / 1001347562

[0056] The nanobubble containing composition can optionally include a scale inhibitor. Suitable scale inhibitors include, but are not limited to, phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonic acids, polyacrylamides, salts of acrylamidomethyl propane sulfonate / acrylic acid copolymer (AMPS / AA), phosphinated maleic copolymer (PHOS / MA), and salts of a polymaleic acid / acrylic acid / acrylamidomethyl propane sulfonate terpolymer (PMA / AA / AMPS). The scale inhibitor can be included in the compositions from about 0.1 to 20 wt. % of the nanobubble containing composition, based on total weight of the composition.

[0057] The nanobubble containing composition can optionally include an emulsifier. Suitable emulsifiers include, but are not limited to, salts of carboxylic acids, products of acylation reactions between carboxylic acids or carboxylic anhydrides and amines, and alkyl, acyl and amide derivatives of saccharides (alkyl-saccharide emulsifiers). The emulsifier can be included in the compositions from about 0.1 to 50 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the nanobubble containing composition, based on total weight of the composition.

[0058] The nanobubble containing composition can optionally include a water clarifier. Suitable water clarifiers include, but are not limited to, inorganic metal salts such as alum, aluminum chloride, and aluminum chlorohydrate, or organic polymers such as acrylic acid based polymers, acrylamide based polymers, polymerized amines, alkanolamines, thiocarbamates, cationic polymers such as diallyldimethylammonium chloride (DADMAC), and epichlorohydrin dimethyl amine. The water clarifier can be included in the compositions from about 0.1 to 50 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %) of the nanobubble containing composition, based on total weight of the composition.

[0059] The nanobubble containing composition can optionally include a dispersant. Suitable dispersants include, but are not limited to, aliphatic phosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonic acid, and aminoalkyl phosphonic acids, e.g. polyaminomethylene phosphonates with 2-10 N atoms e.g. each bearing at least one methylene phosphonic acid group; examples of the latter are ethylenediamine tetra(methylene phosphonate), diethylenetriamine penta(methylene phosphonate), and the triamine- and tetramine-polymethylene phosphonates with 2-4 methylene groups between each N atom, at least 2 of the numbers of methylene groups in each phosphonate being different. Other suitable dispersion agents include lignin, or derivatives of lignin such as lignosulfonate and naphthalene298150774.1 - 15 - CHPX.P0002WO / 1001347562sulfonic acid and derivatives. The dispersant can be included in the nanobubble containing composition from about 0.1 to 50 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9.5 wt. %) of the composition, based on total weight of the composition.

[0060] The nanobubble containing composition can optionally include an emulsion breaker. Suitable emulsion breakers include, but are not limited to, dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds, anionic, cationic and nonionic surfactants, and resins, such as phenolic and epoxide resins. The emulsion breaker can be included in the nanobubble containing composition from about 0.1 to 50 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %) of the composition, based on total weight of the composition.

[0061] The nanobubble containing composition can optionally include a hydrogen sulfide scavenger. Suitable additional hydrogen sulfide scavengers include, but are not limited to, oxidants (e.g., inorganic peroxides such as sodium peroxide or chlorine dioxide); aldehydes (e.g., of 1-10 carbons such as formaldehyde, glyoxal, glutaraldehyde, acrolein, or methacrolein; triazines (e.g., monoethanolamine triazine, monomethylamine triazine, and triazines from multiple amines or mixtures thereof); condensation products of secondary or tertiary amines and aldehydes, and condensation products of alkyl alcohols and aldehydes. The hydrogen sulfide scavenger can be included in the nanobubble containing composition from about 0.5 to 20 wt. % or any range therein (e.g., 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 19.5 wt. %) of the composition, based on total weight of the composition.

[0062] The nanobubble containing composition can optionally include a gas hydrate inhibitor. Suitable gas hydrate inhibitors include, but are not limited to, thermodynamic hydrate inhibitors (THI), kinetic hydrate inhibitors (KHI), and anti-agglomerates (AA). Suitable thermodynamic hydrate inhibitors include, but are not limited to, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, formate brines (e.g. potassium formate), polyols (such as glucose, sucrose, fructose, maltose, lactose, gluconate, monoethylene glycol, diethylene glycol, triethylene glycol, mono-propylene glycol, dipropylene glycol, tripropylene glycols, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, glycerol, diglycerol, triglycerol, and sugar alcohols (e.g. sorbitol, mannitol)), methanol, propanol, ethanol, glycol ethers (such as diethyleneglycol monomethylether, ethyleneglycol monobutylether), and alkyl or cyclic esters of alcohols (such298150774.1 - 16 - CHPX.P0002WO / 1001347562as ethyl lactate, butyl lactate, methylethyl benzoate). The gas hydrate inhibitor can be included in the nanobubble containing compositions from about 0.1 to 25 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 24.5 wt. %) of the composition, based on total weight of the composition.

[0063] The nanobubble containing composition can optionally include a kinetic hydrate inhibitor or anti-agglomerate. Suitable kinetic hydrate inhibitors and anti-agglomerates include, but are not limited to, polymers and copolymers, polysaccharides (such as hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), starch, starch derivatives, and xanthan), lactams (such as polyvinylcaprolactam, polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidone of various molecular weights), surfactants (such as fatty acid salts, ethoxylated alcohols, propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters, polyglycerol esters of fatty acids, alkyl glucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates, alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaine, alkyl amido betaines), hydrocarbon based dispersants (such as lignosulfonates, iminodisuccinates, polyaspartates), amino acids, and proteins. The kinetic hydrate inhibitor can be included in the nanobubble containing composition from about 0.1 to 25 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 24.5 wt. %) of the composition, based on total weight of the composition.

[0064] The nanobubble containing composition can optionally include a biocide. Suitable biocides include, but are not limited to, oxidizing and non-oxidizing biocides. Suitable non-oxidizing biocides include, for example, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein), amine-type compounds (e.g., quaternary amine compounds and cocodiamine), halogenated compounds (e.g., 2-bromo-2-nitropropane-3-diol (Bronopol) and 2-2-dibromo-3- nitrilopropionamide (DBNPA)), sulfur compounds (e.g., isothiazolone, carbamates, and metronidazole), and quaternary phosphonium salts (e.g., tetrakis(hydroxymethyl)- phosphonium sulfate (THPS)). Suitable oxidizing biocides include, for example, sodium hypochlorite, trichloroisocyanuric acids, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorinated hydantoins, stabilized sodium hypobromite, activated sodium bromide, brominated hydantoins, chlorine dioxide, ozone, and peroxides. The biocide can be included in the nanobubble containing composition from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the composition, based on total weight of the composition.298150774.1 - 17 - CHPX.P0002WO / 1001347562

[0065] The nanobubble containing composition can optionally include a pH modifier. Suitable pH modifiers include, but are not limited to, alkali hydroxides, alkali carbonates, alkali bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, acidic pH modifiers (e.g., mineral and / or organic acids), and mixtures or combinations thereof. Exemplary pH modifiers include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium oxide, and magnesium hydroxide. The pH modifier can be included in the nanobubble containing composition from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the composition, based on total weight of the composition.

[0066] The nanobubble containing composition can optionally include a polymer. The nanobubble containing composition can also include one or more polymers. The polymer can be included in the compositions from about 0.1 to 50 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %) of the composition. In some particular, aspects, the polymer can be included in the compositions from about 0.5 to 10 wt. % of the composition, or from about 0.5 to 5 wt. % of the composition, based on total weight of the composition. Suitable polymers may include, but are not limited to, drag reducing agents, viscosifers, interfacial tension reducers, wettability agents. Polymers may be used to improve and / or enhance oil recovery, improve injectability of other agents, and reduce friction.

[0067] The nanobubble containing composition can optionally include a surfactant. The nanobubble containing composition can also include one or more surfactants. The surfactant can be included in the compositions from about 0.1 to 50 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %) of the composition. In some particular, aspects, the surfactant can be included in the compositions from about 0.5 to 10 wt. % of the composition, or from about 0.5 to 5 wt. % of the composition, based on total weight of the composition. Suitable surfactants include, but are not limited to, anionic surfactants, nonionic surfactants, cationic surfactants, and / or amphoteric surfactants.298150774.1 - 18 - CHPX.P0002WO / 1001347562B. Nanobubble Containing Composition (Non-Aqueous Continuous Phase) 1. Non-Aqueous Continuous Phase

[0068] A nanobubble containing composition can include a non-aqueous continuous phase (e.g., an organic solvent). Unlike the nanobubble containing composition that includes an aqueous continuous phase, the gas-filled nanobubbles of the present disclosure remain dispersed in the non-aqueous continuous phase (e.g., an organic solvent, without the salinity associated with an aqueous continuous phase). 2. Discontinuous Phase

[0069] The nanobubble containing composition can include a discontinuous phase comprising a plurality of gas-filled nanobubbles. In some aspects, such nanobubbles can have an average diameter 1 nm to up to 1000 nm or any range or number therein (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 960, 970, 980, 990, 991, 992, 993, 994, 995, 996, 997, 998, or 999 nm). In some preferred aspects, the nanobubbles have an average size of 20 nm to 500 nm. The discontinuous phase is dispersed in the non- aqueous continuous phase. 3. Nanobubble Stabilizer

[0070] The nanobubble containing composition can include a nanobubble stabilizer such as those described throughout this specification. In some aspects, the nanobubble containing composition can include a nanobubble stabilizer, such as 1 parts per million (ppm) to 50,000 ppm or any range or number therein (e.g., 2, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 5000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 46,000, 47,000, 48,000, 49,000, 49,500, 49,900 ppm) of the nanobubble stabilizer. The nanobubble stabilizer can include without limitation any of various types of materials that can stabilize the nanobubbles in a composition. This stabilizing can occur by the nanobubble stabilizer adsorbing onto a surface of the nanobubble. In certain aspects, the adsorption can be the nanobubble stabilizer attaching to a surface of the nanobubble. The attachment can be through an ionic bond, a covalent bond, a hydrogen bond, a Van der Walls interaction, or hydrophobic interactions between the stabilizer and the surface of the nanobubble.298150774.1 - 19 - CHPX.P0002WO / 10013475624. Functional Ingredient(s)

[0071] In various embodiments, the nanobubble containing composition can (optionally) include one or more additional functional ingredients. The functional ingredients can provide desired properties and functionalities to the nanobubble containing composition.

[0072] In some embodiments, the nanobubble containing composition may include additional corrosion inhibitors, surfactants, polymers, pH modifiers, surfactants, hydrate inhibitors, scale inhibitors, biocides, salt substitutes, relative permeability modifiers, sulfide scavengers, breakers, asphaltene inhibitors, paraffin inhibitors, metal complexing agents (chelants), emulsifiers or coupling agents, demulsifiers, iron control agents, friction reducers, drag reducing agents, flow improvers, viscosity reducers, stability component, and the like. Exemplary types of the various additional functional ingredients is included in U.S. Patent No. 11,242,480, which is incorporated by reference in its disclosure of the various listings of additional functional ingredients.

[0073] In further embodiments, the nanobubble containing composition may include at least one additional component selected from the group consisting of additional corrosion inhibitors, pH modifiers, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, metal complexing agents (chelants), surfactants, emulsifiers or coupling agents, water clarifiers, dispersants, emulsion breakers and combinations thereof.

[0074] According to embodiments of the disclosure, the various additional functional ingredients may be provided in the nanobubble containing composition in an amount from about 0 wt. % and about 40 wt. %, from about 0 wt. % and about 30 wt. %, from about 0 wt. % and about 20 wt. %, from about 0.01 wt. % and about 40 wt. %, from about 0.1 wt. % and about 40 wt. %, from about 0.1 wt. % and about 30 wt. %, from about 0.1 wt. % and about 20 wt. %, or from about 1 wt. % and about 2 wt. %, or from about 1 wt. % and about 10 wt. %. In some aspects, the nanobubble containing composition can include 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt. %, or any range or number therein, based on the total weight of the composition, of a functional ingredient or combination of functional ingredients. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range. Additional examples of additional functional ingredients are listed herein as exemplary wt. % ranges based on the total weight of the nanobubble containing composition, in addition these weight percentage ranges.298150774.1 - 20 - CHPX.P0002WO / 1001347562

[0075] The nanobubble containing composition can optionally include an organic sulfur compound, such as a mercaptoalkyl alcohol, mercaptoacetic acid, thioglycolic acid, 3,3′- dithiodipropionic acid, thiosulfate, thiourea, L-cysteine, or tert-butyl mercaptan. An exemplary mercaptoalkyl alcohol comprises 2-mercaptoethanol. The organic sulfur compound can be included in the nanobubble containing compositions from about 0 to about 15 wt. % or any range or number therein (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 wt. %) of the composition.

[0076] The nanobubble containing composition can optionally include a demulsifier. An exemplary demulsifier comprises an oxyalkylate polymer, such as a polyalkylene glycol. The demulsifier can be included in the nanobubble containing composition from about 0 to 5 wt. % or any range or number therein (e.g., 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 wt. %) of the composition, based on total weight of the composition.

[0077] The nanobubble containing composition can optionally include an asphaltene inhibitor. Suitable asphaltene inhibitors include, but are not limited to, aliphatic sulfonic acids; alkyl aryl sulfonic acids; aryl sulfonates; lignosulfonates; alkylphenol / aldehyde resins and similar sulfonated resins; polyolefin esters; polyolefin imides; polyolefin esters with alkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefin amides; polyolefin amides with alkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefin imides with alkyl, alkylenephenyl or alkylenepyridyl functional groups; alkenyl / vinyl pyrrolidone copolymers; graft polymers of polyolefins with maleic anhydride or vinyl imidazole; hyperbranched polyester amides; polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkyl succinates, sorbitan monooleate, and polyisobutylene succinic anhydride. The asphaltene inhibitor can be included in the compositions from about 0.1 to 10 wt.% or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the composition, based on total weight of the composition.

[0078] The nanobubble containing composition can optionally include a paraffin inhibitor. Suitable paraffin inhibitors include, but are not limited to, paraffin crystal modifiers, and dispersant / crystal modifier combinations. Suitable paraffin crystal modifiers include, but are not limited to, alkyl acrylate copolymers, alkyl acrylate vinylpyridine copolymers, ethylene vinyl acetate copolymers, maleic anhydride ester copolymers, branched polyethylenes, naphthalene, anthracene, microcrystalline wax and / or asphaltenes. Suitable dispersants include, but are not limited to, dodecyl benzene sulfonate, oxyalkylated alkylphenols, and oxyalkylated alkylphenolic resins. The paraffin inhibitor can be included in the nanobubble containing compositions from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4,298150774.1 - 21 - CHPX.P0002WO / 10013475620.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the composition, based on total weight of the composition.

[0079] The nanobubble containing composition can optionally include a scale inhibitor. Suitable scale inhibitors include, but are not limited to, phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonic acids, polyacrylamides, salts of acrylamidomethyl propane sulfonate / acrylic acid copolymer (AMPS / AA), phosphinated maleic copolymer (PHOS / MA), and salts of a polymaleic acid / acrylic acid / acrylamidomethyl propane sulfonate terpolymer (PMA / AA / AMPS). The scale inhibitor can be included in the compositions from about 0.1 to 20 wt. % of the nanobubble containing composition, based on total weight of the composition.

[0080] The nanobubble containing composition can optionally include an emulsifier. Suitable emulsifiers include, but are not limited to, salts of carboxylic acids, products of acylation reactions between carboxylic acids or carboxylic anhydrides and amines, and alkyl, acyl and amide derivatives of saccharides (alkyl-saccharide emulsifiers). The emulsifier can be included in the compositions from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the nanobubble containing composition, based on total weight of the composition.

[0081] The nanobubble containing composition can optionally include a water clarifier. Suitable water clarifiers include, but are not limited to, inorganic metal salts such as alum, aluminum chloride, and aluminum chlorohydrate, or organic polymers such as acrylic acid based polymers, acrylamide based polymers, polymerized amines, alkanolamines, thiocarbamates, cationic polymers such as diallyldimethylammonium chloride (DADMAC), and epichlorohydrin dimethyl amine (EPI DMA). The water clarifier can be included in the compositions from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the nanobubble containing composition, based on total weight of the composition.

[0082] The nanobubble containing composition can optionally include a dispersant. Suitable dispersants include, but are not limited to, aliphatic phosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonic acid, and aminoalkyl phosphonic acids, e.g. polyaminomethylene phosphonates with 2-10 N atoms e.g. each bearing at least one methylene phosphonic acid group; examples of the latter are ethylenediamine tetra(methylene phosphonate), diethylenetriamine penta(methylene phosphonate), and the triamine- and tetramine-polymethylene phosphonates with 2-4 methylene groups between each N atom, at least 2 of the numbers of methylene groups in each phosphonate being different. Other suitable298150774.1 - 22 - CHPX.P0002WO / 1001347562dispersion agents include lignin, or derivatives of lignin such as lignosulfonate and naphthalene sulfonic acid and derivatives. The dispersant can be included in the nanobubble containing composition from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9.5 wt. %) of the composition, based on total weight of the composition.

[0083] The nanobubble containing composition can optionally include an emulsion breaker. Suitable emulsion breakers include, but are not limited to, dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds, anionic, cationic and nonionic surfactants, and resins, such as phenolic and epoxide resins. The emulsion breaker can be included in the nanobubble containing composition from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9.5 wt. %) of the composition, based on total weight of the composition.

[0084] The nanobubble containing composition can optionally include a hydrogen sulfide scavenger. Suitable additional hydrogen sulfide scavengers include, but are not limited to, oxidants (e.g., inorganic peroxides such as sodium peroxide or chlorine dioxide); aldehydes (e.g., of 1-10 carbons such as formaldehyde, glyoxal, glutaraldehyde, acrolein, or methacrolein; triazines (e.g., monoethanolamine triazine, monomethylamine triazine, and triazines from multiple amines or mixtures thereof); condensation products of secondary or tertiary amines and aldehydes, and condensation products of alkyl alcohols and aldehydes. The hydrogen sulfide scavenger can be included in the nanobubble containing composition from about 0.5 to 20 wt. % or any range therein (e.g., 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 19.5 wt. %) of the composition, based on total weight of the composition.

[0085] The nanobubble containing composition can optionally include a gas hydrate inhibitor. Suitable gas hydrate inhibitors include, but are not limited to, thermodynamic hydrate inhibitors (THI), kinetic hydrate inhibitors (KHI), and anti-agglomerates (AA). Suitable thermodynamic hydrate inhibitors include, but are not limited to, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, formate brines (e.g. potassium formate), polyols (such as glucose, sucrose, fructose, maltose, lactose, gluconate, monoethylene glycol, diethylene glycol, triethylene glycol, mono-propylene glycol, dipropylene glycol, tripropylene glycols, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, glycerol, diglycerol, triglycerol, and sugar alcohols (e.g. sorbitol, mannitol)), methanol, propanol, ethanol, glycol ethers (such as diethyleneglycol monomethylether, ethyleneglycol monobutylether), and alkyl or cyclic esters of alcohols (such298150774.1 - 23 - CHPX.P0002WO / 1001347562as ethyl lactate, butyl lactate, methylethyl benzoate). The gas hydrate inhibitor can be included in the nanobubble containing compositions from about 0.1 to 25 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 24.5 wt. %) of the composition, based on total weight of the composition.

[0086] The nanobubble containing composition can optionally include a kinetic hydrate inhibitor or anti-agglomerate. Suitable kinetic hydrate inhibitors and anti-agglomerates include, but are not limited to, polymers and copolymers, polysaccharides (such as hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), starch, starch derivatives, and xanthan), lactams (such as polyvinylcaprolactam, polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidone of various molecular weights), surfactants (such as fatty acid salts, ethoxylated alcohols, propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters, polyglycerol esters of fatty acids, alkyl glucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates, alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaine, alkyl amido betaines), hydrocarbon based dispersants (such as lignosulfonates, iminodisuccinates, polyaspartates), amino acids, and proteins. The kinetic hydrate inhibitor can be included in the nanobubble containing composition from about 0.1 to 25 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 24.5 wt. %) of the composition, based on total weight of the composition.

[0087] The nanobubble containing composition can optionally include a biocide. Suitable biocides include, but are not limited to, oxidizing and non-oxidizing biocides. Suitable non-oxidizing biocides include, for example, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein), amine-type compounds (e.g., quaternary amine compounds and cocodiamine), halogenated compounds (e.g., 2-bromo-2-nitropropane-3-diol (Bronopol) and 2-2-dibromo-3- nitrilopropionamide (DBNPA)), sulfur compounds (e.g., isothiazolone, carbamates, and metronidazole), and quaternary phosphonium salts (e.g., tetrakis(hydroxymethyl)- phosphonium sulfate (THPS)). Suitable oxidizing biocides include, for example, sodium hypochlorite, trichloroisocyanuric acids, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorinated hydantoins, stabilized sodium hypobromite, activated sodium bromide, brominated hydantoins, chlorine dioxide, ozone, and peroxides. The biocide can be included in the nanobubble containing composition from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the composition, based on total weight of the composition.298150774.1 - 24 - CHPX.P0002WO / 1001347562

[0088] The nanobubble containing composition can optionally include a pH modifier. Suitable pH modifiers include, but are not limited to, alkali hydroxides, alkali carbonates, alkali bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates and mixtures or combinations thereof. Exemplary pH modifiers include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium oxide, and magnesium hydroxide. The pH modifier can be included in the nanobubble containing composition from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the composition, based on total weight of the composition.

[0089] The nanobubble containing composition can optionally include a surfactant. The nanobubble containing composition can also include one or more surfactants. The surfactant can be included in the compositions from about 0.1 to 10 wt. % or any range therein (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 9.5 wt. %) of the composition. In some particular, aspects, the surfactant can be included in the compositions from about 0.5 to 10 wt. % of the composition, or from about 0.5 to 5 wt. % of the composition, based on total weight of the composition. Suitable surfactants include, but are not limited to, anionic surfactants, nonionic surfactants and / or amphoteric surfactants. C. Methods of Forming the Nanobubbles 1. Commercially Available Equipment

[0090] In various embodiments, the gas-filled nanobubbles of the present disclosure may be formed by subjecting a particular active material (e.g., various oilfield chemistries, etc.) using a commercially available nanobubble generator. In some embodiments, the commercially available equipment may be run with clean air (or other gasses as necessary) as the gas at 2 cubic feet per hour (CFH) with 10 minutes of reaction time. 2. Syringe NB

[0091] Another example method of forming nanobubbles is by an “expansion- compression” method (as described in the journal Nanoscale, entitled “A Henry's law method for generating bulk nanobubbles,” available at https: / / doi.org / 10.1039 / D0NR03332D), also known as “syringe method”. In various embodiments, the gas-filled nanobubbles of the present disclosure may be formed by subjecting a particular active material (e.g., various oilfield chemistries, etc.) using the above-mentioned “expansion-compression” method, also known as “syringe method”. As an illustrative example, the syringe method may be utilized to fill a 50298150774.1 - 25 - CHPX.P0002WO / 1001347562mL syringe to the 30 mL mark. The slip tip (which allows a needle to be quickly and conveniently pushed straight on to the end of the tip, if a needle is utilized) may be capped with a rubber septum, and the septum may be taped to the syringe. The syringe may then be pulled back as far as possible and then released. This is referred to as the “one pull” method. In a preferred embodiment, the nanobubbles may be generated with 5 pulls or more. 3. Sonic Probe

[0092] In some embodiments, the gas-filled nanobubbles of the present disclosure may be formed using a sonicator. For example, a particular active material (e.g., various oilfield chemistries, etc.) may be subjected to a sonic probe operating at 20 kHz. The amplitude and contact time for the sonic probe may be optimized for generating the gas-filled nanobubbles of the present disclosure. 4. Nanobubble Size and Concentration Measurement

[0093] For all methods, nanobubble size and concentration was measured using a Nanosight NS300 made by Malvern Panalytical Ltd (a Spectra company). D. Methods of Using the Nanobubble Containing Compositions

[0094] In various aspects, the nanobubble containing compositions of the present disclosure may be utilized for various applications, including but not limited to various oilfield chemistries.

[0095] As an example, a method of using the nanobubble containing compositions of the present disclosure may include contacting the nanobubble containing composition with a second composition and / or system. For example, the second composition and / or system may include hydrocarbons (e.g., where the hydrocarbons are comprised in a subterranean formation, produced oil, liquid condensate, or combinations thereof), water (such as in the formation, or production fluids, and others) and / or related systems (e.g., hydrogen systems, CO2systems, upstream systems, midstream applications, downstream systems, mixed systems, and combinations thereof). In some aspects, the method may include contacting the nanobubble containing composition (e.g., one having an aqueous continuous phase) with the hydrocarbons such that the gas-filled nanobubbles enter into an interstitial space defined between the hydrocarbons and the subterranean formation to reduce interfacial tension between the hydrocarbons and the subterranean formation. In some aspects, the nanobubble stabilizer of the nanobubble containing composition can include an oil recovery composition comprising a blend of an amphoteric surfactant and a non-ionic surfactant. In such cases, contacting the nanobubble containing composition (including the oil recovery composition) with the298150774.1 - 26 - CHPX.P0002WO / 1001347562hydrocarbons may result in enhanced oil recovery from the subterranean formation, as further described herein with respect to Example 1 below. Such an enhanced oil recovery from the subterranean formation may correspond to a faster rate of oil recovery relative to the oil recovery composition alone.

[0096] As another example, the method may include contacting a nanobubble containing composition of the present invention with an alternative second composition, including production chemicals such as corrosion inhibitors, asphaltene inhibitors, emulsion breakers, paraffin inhibitors, scale inhibitors, H2S scavengers, and fracking fluids. As yet another example, the method may include contacting a nanobubble containing composition of the present invention with polymer as the second composition.

[0097] In the case of a corrosion inhibitor, a combination of the nanobubble containing composition of the present disclosure and the corrosion inhibitor can result in a reduced corrosion rate relative to the corrosion inhibitor alone (i.e., without the stabilized nanobubbles). In such cases, contacting the nanobubble containing composition (including the corrosion inhibitor) with the hydrocarbons may result in enhanced corrosion inhibition, as further described herein with respect to Example 2 below.

[0098] Another example of a method of use for the nanobubble containing compositions of the present disclosure include utilization with an asphaltene inhibitor that can result in a reduced asphaltene deposition rate relative to the asphaltene inhibitor composition alone (i.e., without the stabilized nanobubbles).

[0099] Other examples of methods of use for the nanobubble containing compositions of the present disclosure may include utilization with an emulsion breaking material or potentially with a paraffin inhibition material.

[0100] It will be appreciated that there may be a variety of other potential methods of use for the nanobubble containing compositions of the present disclosure. As illustrative, non- limiting examples, the nanobubble containing compositions of the present invention may be advantageous when utilized in one or more the following processes / applications: wastewater treatment; wastewater and sewer management; water treatment; food sanitation; carpet cleaning; building cleaning; diaper cleaning; dry cleaning; fur cleaning; jewelry cleaning; leather cleaning; carpet cleaning; window cleaning; pool cleaning; motor vehicle (car, truck, bus, bicycle, motorcycle, etc.) cleaning; train cleaning; ship cleaning; aircraft cleaning; oil and gas well treatment; oil refining; fuel treatment; and steam assisted gravity drainage.298150774.1 - 27 - CHPX.P0002WO / 1001347562EXAMPLES

[0101] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results. A. Example 1

[0102] The product used in this example is a blend of an amphoteric surfactant ( lauryl hydroxysultaine or lauryl sultaine) and a nonionic surfactant (Surfonic L12-3 (CAS # 66455- 15-0) along with demulsifiers to help prevent emulsions from forming. This product was used at 1000 ppm active material. The 1000 ppm active material was subjected to nanobubbles, using the commercially available equipment and an expansion-compression method (also known as syringe method). The commercially available equipment was run with clean air as the gas at 2 cubic CFH with 10 minutes of reaction time. The syringe method filled a 50 mL syringe to the 30 mL mark, the slip tip was capped with a rubber septum, the septum was taped to the syringe then the syringe was pulled back as far as possible then released (e.g., a “one pull”). For this experiment, the nanobubbles were generated with 5 pulls. Nanobubble size and concentration was measured using a Nanosight NS300 made by Malvern.

[0103] An imbibition test was done by saturating an outcrop core (one that has not been exposed to oil) with an oil of interest. The weight of the core is measured before and after saturation then the density of the oil is used to calculate the volume of oil saturated. The saturated cores are placed into Amott cells, the solution of interest is added to the cell then the cell is capped and placed into an oil bath at the reservoir temperature for the oil. The amount of oil released is then read on the graduated neck of the cell. The oil recovered is compared to just water and to the Surfactant Blend solution alone.

[0104] With respect to Example 1, FIG. 1 depicts comparative experimental testing data associated with the effects of nanobubbles on oil recovery percentage over time.

[0105] Referring to FIG. 1, five lines are depicted (in grayscale) corresponding to: “Water” (represented by diamond icons); “Nanobubble Generator NB” (represented by square icons); “Syringe NB” (represented by triangle icons); “Surfactant Blend 1000 ppm” (represented by a first set of X icons, corresponding to the lower line in FIG. 1); “Surfactant Blend + Nanobubble Generator NB” (represented by a second set of X icons, corresponding to the upper line in FIG. 1, with the rapid increase in oil recovery percentage after a time period298150774.1 - 28 - CHPX.P0002WO / 1001347562of approximately 25 hours); and “Surfactant Blend + Syringe NB” (represented by a circular icon).

[0106] Of particular note in FIG.1 is the divergence between the active material alone (Surfactant Blend 1000 ppm) and the active material with the stabilized gas-filled nanobubbles (Surfactant Blend + Nanobubble Generator NB). FIG. 1 illustrates one example of a nanobubble containing composition of the present disclosure having an aqueous continuous phase, with the surfactants in the Surfactant Blend material acting as the nanobubble stabilizer. As shown in the experimental results data in FIG.1, the gas-filled nanobubbles did not rapidly coalesce but instead appear to remain dispersed in the aqueous continuous phase for an extended period of time.

[0107] Thus, the inventors have discovered a novel method of generating stabilized gas-filled nanobubbles such that when the nanobubble containing composition containing such stabilized nanobubbles clearly results in enhanced oil recovery (EOR), as represented as “Surfactant Blend + Nanobubble Generator NB” relative to the stand-alone active material “Surfactant Blend 1000 ppm” depicted in FIG.1. Without wishing to be bound by theory, by contacting the nanobubble containing composition of Example 1 with hydrocarbons (e.g., in a subterranean formation), the gas-filled nanobubbles may enter into an interstitial space defined between the hydrocarbons and the subterranean formation to reduce interfacial tension between the hydrocarbons and the subterranean formation. Without wishing to be bound by theory, such a reduction in interfacial tension may result in the enhanced oil recovery as dramatically depicted in the steep rise of the nanobubble containing composition represented as “Surfactant Blend + Nanobubble Generator NB” illustrated in FIG. 1. While the experimental setup for Example 1 corresponded to an imbibition test (i.e., not in an actual subterranean formation), the enhanced oil recovery rate associated with the experimental setup is strongly indicative of the nanobubble containing composition of Example 1 resulting in a faster rate of oil recovery when utilized in an actual subterranean formation relative to the oil recovery composition (“Surfactant Blend 1000 ppm”). B. Example 2

[0108] Corrosion tests were performed using pre-weighed C1018 mild steel coupons (1 / 4" X 73 / 8") with sandblast finish in a wheel box. The coupon was dipped for about 5 seconds in the blend under assessment and allowed to drip for 10 seconds to allow for excess product to be removed. The coupon was placed in a vessel containing CO2saturated fluids of 3% NaCl brine without liquid hydrocarbon and closed. The vessel was then mounted on a wheel in a298150774.1 - 29 - CHPX.P0002WO / 1001347562temperature-controlled cabinet at 60 °C. The wheel was rotated at 26 rpm. After 24 hours (h) and then again at 48h and 72h, the fluids were replaced with chemical-free brine and were run for a further 24h. After the last brine replenishment at 72h, the test was continued for a further 24h to a total of 96h. After the test, the coupons were removed from the vessel, cleaned and re-weighed and the corrosion rate determined by weight loss and the percentage inhibition determined by comparison to a blank (i.e. a test carried out under otherwise the same conditions but in the absence of any chemical treatment).

[0109] Tests were carried out two ways – one using the original CI blend with or without infused with nanobubbles (NB) and then a second set taking just 1% of the CI blend with or without infused with nanobubbles and diluting with solvent. This was to help with possible differentiation. Each test was performed in duplicate. Average percent inhibition from the two tests is given in Table 1 below. Table 1: Infused Inhibitor CI Blend with Corrosi % Average % N l on Rate P i P i / A.1.1.5.2.1.7.7.9, . , . ** CI2 is 10.3 benzyl chloride quaternized alkyl pyridine, ~14.3% C12-C18 benzyl quarternary ammonium compounds, ~6% mercaptoethanol, ~4% ethoxylated nonly phenol phosphate ester, ~2% oxyalkylated polymer demulsifier, ~13.5% EGMBE, balance water.298150774.1 - 30 - CHPX.P0002WO / 1001347562***solvent is water.

[0110] Thus, the inventors have discovered a novel method of generating stabilized gas-filled nanobubbles such that when the nanobubble containing composition containing such stabilized nanobubbles clearly results in a reduced corrosion rate, as represented in Table 1. C. Example 3

[0111] With respect to Emulsion Breaking, a standard bottle test was performed as follows: 1) Confirm dryness of oil sample before use by completing grind out using 50 / 50 oil: xylenes; 2) Add 117ml of dry crude oil and 3ml of synthetic brine to a 16 oz. glass jar- repeat 3 times; 3) Place samples in the water bath at 70°C for approximately 30 minutes; 4) After reaching test temperature, remove from water bath, and homogenize with ultraturrax at 5,000 rpm for 5 minutes. Visually inspect to ensure complete mixing was accomplished; 5) Transfer 100ml of emulsion to graduated conical tube; 6) Inspect for separation or change (these tubes should look identical) and take picture; 7) Inject 500ppm of neat Emulsion Breaker to bottle 2, 500ppm of Nano Bubble Emulsion Breaker to bottle 3; 8) Cap tubes and handshake 100X (hard shakes); Bottles cool during agitation with ultraturrax; and 9) Record water drop at regular intervals out to 30 (adjusted to 60) minutes; take pictures at the end of the test for comparison and note water quality and interface (can optionally extend).

[0112] The inventors have noted that experimental data was indicative of quicker water drop and sharper interface (with nanobubbles) for this particular use case. Specifically, the inventors recorded a water drop of 2.2 mL (with nanobubbles) compared to a water drop of 1.0 mL (without nanobubbles). D. Example 4

[0113] Nanobubbles (NB) were imparted on chemical samples in two ways. The first way was by using an expansion-contraction method (also known as the syringe method). A syringe was filled halfway (for example, a 30 mL syringe was filled with 15 mL of corrosion inhibitor) then was capped. The plunger was pulled back as far as possible creating a vacuum. The syringe was released, forcing the gas into the liquid. This process is one cycle. The samples listed in Table 2 below were processed for 5 cycles before being tested. The second way was by using a Qsonica 20 kHz sonic probe set at 50% amplitude (sonic intensity) for 5 minutes. Due to the heat generated during sonication, all samples were placed in an ice water bath to minimize evaporation or heating.

[0114] Wheel box corrosion tests were performed on samples with no corrosion inhibitor (blank), samples treated with corrosion inhibitor only, samples treated with corrosion298150774.1 - 31 - CHPX.P0002WO / 1001347562inhibitor with nanobubbles imparted by the expansion-contraction method and samples of corrosion inhibitor with nanobubbles imparted by the sonic probe method. Results are shown in Tables 2-3 and FIGs. 2-6. Table 3 shows the results in Table 2 and a comparison between chemical treatment without nanobubbles to the chemical treatment infused with nanobubbles. Table 2: Chemical Product Infused with Corrosi% Nanobubbles (Yes / No)on Rate (MPY)Protection Blank No 18.6 0 n n n nTable 3: % Improvement t298150774.1 - 32 - CHPX.P0002WO / 1001347562JJM / 10102 / 116A Syringe Yes – sparged9.21 NB6.9 63nt t nt t nt t nt t, , .298150774.1 - 33 - CHPX.P0002WO / 1001347562E. Other Examples (Prophetic)

[0115] The inventors have identified at least the following other applications where nanobubbles could possibly improve the underlying chemistries: Gas Lift; H2S Scavenging; Scale Inhibition; Reverse Emulsion Breaking / Phase Separation; Cleaning Applications (e.g., pipelines, biofilms, reverse osmosis membranes, etc.).

[0116] For gas lift, the inventors expect that a foam test may be used to determine whether a “foamer” with nanobubbles would be more effective than one without nanobubbles in terms of removing liquid loading.

[0117] For reverse emulsion breaking / water clarification, the inventors expect that a bottle test may be used to determine whether products containing nanobubbles are more effective (either quicker acting or at a lower dose) than ones without nanobubbles.

[0118] For membrane cleaning, the inventors expect that a test of a traditional membrane cleaner against “Water plus NB” may be used to determine which one would be more effective. Essentially, the test would involve a tank filled with water or chemical which is recycled through the membrane for a specified time frame. Effectiveness can be determined by measuring the pressure through the membrane. ******

[0119] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.298150774.1 - 34 - CHPX.P0002WO / 1001347562

Claims

CLAIMS 1. A nanobubble containing composition comprising: an aqueous continuous phase; a discontinuous phase comprising a plurality of gas-filled nanobubbles; and a nanobubble stabilizer, wherein the discontinuous phase is dispersed in the aqueous continuous phase, and wherein the gas-filled nanobubbles remain dispersed in the aqueous continuous phase.

2. The nanobubble containing composition of claim 1, wherein the aqueous continuous phase has a total dissolved solids level of at least 100 parts per million (ppm).

3. A nanobubble containing composition comprising: a non-aqueous continuous phase; a discontinuous phase comprising a plurality of gas-filled nanobubbles; and a nanobubble stabilizer, wherein the discontinuous phase is dispersed in the non-aqueous continuous phase, and wherein the gas-filled nanobubbles remain dispersed in the non-aqueous continuous phase.

4. A nanobubble containing composition comprising: an emulsion comprising an aqueous phase and a non-aqueous phase; a plurality of gas-filled nanobubbles; and at least one surfactant that causes the gas-filled nanobubbles to remain dispersed in the emulsion.

5. The nanobubble containing composition of any one of claims 1 to 4, wherein the nanobubble stabilizer includes one or more materials that adsorb onto a surface of individual gas-filled nanobubbles of the plurality of gas-filled nanobubbles.

6. The nanobubble containing composition of any one of claims 1 to 4, wherein the nanobubble stabilizer includes one or more materials that attach onto a surface of individual gas-filled nanobubbles of the plurality of gas-filled nanobubbles.

7. The nanobubble containing composition of claim 1, wherein the nanobubble stabilizer comprises at least one of an amphoteric surfactant and a non-ionic surfactant.298150774.1 - 35 - CHPX.P0002WO / 10013475628. The nanobubble containing composition of claim 7, wherein the nanobubble stabilizer includes a blend of the amphoteric surfactant and the non-ionic surfactant, preferably wherein the amphoteric surfactant comprises lauryl hydroxysultaine or lauryl sultaine, and the nonionic surfactant comprises Surfonic L12-3 (CAS # 66455-15-0).

9. The nanobubble containing composition of claim 8, wherein an oil recovery composition includes the blend, and wherein the blend further comprises one or more demulsifiers.

10. The nanobubble containing composition of any one of claims 1 to 4, wherein the nanobubble stabilizer comprises a cationic surfactant.

11. The nanobubble containing composition of claim 10, wherein the cationic surfactant is benzalkonium chloride.

12. The nanobubble containing composition of claim 10, wherein a corrosion inhibition composition includes the cationic surfactant, and wherein the corrosion inhibition composition further comprises a corrosion inhibitor.

13. A method comprising: contacting the nanobubble containing composition of any one of claims 1 to 4 with a second composition.

14. The method of claim 13, wherein the second composition comprises hydrocarbons.

15. The method of claim 14, wherein the hydrocarbons are comprised in a subterranean formation.

16. The method of claim 15, wherein the method includes contacting the nanobubble containing composition of claim 1 with the hydrocarbons such that the gas-filled nanobubbles enter into an interstitial space defined between the hydrocarbons and the subterranean formation to reduce interfacial tension between the hydrocarbons and the subterranean formation.

17. The method of claim 16, wherein the nanobubble stabilizer of the nanobubble containing composition of claim 1 includes an oil recovery composition comprising a blend of an amphoteric surfactant and a non-ionic surfactant.298150774.1 - 36 - CHPX.P0002WO / 100134756218. The method of claim 17, wherein contacting the nanobubble containing composition of claim 1 with the hydrocarbons results in enhanced oil recovery from the subterranean formation.

19. The method of claim 18, wherein the enhanced oil recovery from the subterranean formation corresponds to a faster rate of oil recovery relative to the oil recovery composition comprising the blend of the amphoteric surfactant and the non-ionic surfactant.

20. The method of claim 14, wherein the hydrocarbons are comprised in produced oil, liquid condensate, or a combination thereof.

21. The method of claim 13, wherein the second composition comprises water in a subterranean formation or in a production fluid.

22. The method of claim 13, wherein the second composition is associated with a hydrogen system, a carbon dioxide system, an upstream system, a downstream system, a mixed upstream / downstream system, or any combination thereof.

23. The method of claim 13, wherein the second composition comprises one or more production chemicals.

24. The method of claim 13, wherein the second composition comprises polymer.

25. The method of claim 5, wherein the second composition comprises an asphaltene inhibitor, and wherein the method includes contacting the nanobubble containing composition of claim 3 with the asphaltene inhibitor.

26. The method of claim 25, wherein a combination of the nanobubble containing composition of claim 3 and the asphaltene inhibitor results in a reduced asphaltene deposition rate relative to a composition that includes the asphaltene inhibitor but does not include the gas-filled nanobubbles.

27. The method of claim 26, wherein the second composition comprises an emulsion breaking material, and wherein the method includes contacting the nanobubble containing composition of claim 3 with the emulsion breaking material.298150774.1 - 37 - CHPX.P0002WO / 100134756228. The method of claim 27, wherein a combination of the nanobubble containing composition of claim 3 and the emulsion breaking material results in a faster water drop and sharper interface relative to a composition that includes the emulsion breaking material but does not include the gas-filled nanobubbles.298150774.1 - 38 - CHPX.P0002WO / 1001347562

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