Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations

Abstract

To provide a reverse emulsion breaker composition for breaking reverse emulsion commonly found in a produced fluid in oil and gas operations.SOLUTION: A novel class of multiple charged cationic or anionic compounds that are derived from an aza-Michael Addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) is prepared and used. The disclosed reverse emulsion breaking methods or compositions are found to be more effective than those methods or compositions including those commonly used for oil / solid and water separation. The activated olefin (Michael acceptor) has an ionic group according to one of the following formulas (I), (II), (III), wherein X is NH or O.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. § 119 to Provisional Application No. 62 / 724,398, filed Aug. 29, 2018, the entirety of which is incorporated herein by reference.

[0002] The present disclosure generally relates to the field of multiply charged cationic or anionic compounds, methods of making them, and their uses. The disclosure also generally relates to the field of using inverse emulsion breaking compositions in oil and gas operations. In particular, the disclosure relates to a novel class of multiply charged cationic or anionic compounds derived from the aza-Michael addition reaction between polyamines (Michael donors) and activated olefins (Michael acceptors), methods of making them, and their uses. The disclosed multiply charged cationic or anionic compounds or salts thereof have at least two or three positive or negative charges in each molecule. The disclosure also relates to breaking oil-in-water emulsions or multiple emulsions in production fluids in oil and gas operations using inverse emulsion breaking compositions comprising one or more of the multiply charged cationic or anionic compounds disclosed herein. The methods, inverse emulsion breaking compositions, and multiply charged cationic or anionic compounds disclosed herein are more effective at separating oil from water than methods, compositions, or compounds currently used in oil and gas operations. [Background technology]

[0003] Oil-in-water and water-in-oil-in-water emulsions may occur in many industrial systems. For example, production fluids containing emulsified oil, such as inverse or oil-in-water emulsions, and complex emulsions containing dispersed solids are common in oil and gas operations.

[0004] In particular, in steam-assisted gravity drainage (SAGD) operations, steam is injected into the formation to stimulate the production of bitumen or heavy hydrocarbons, creating oil-in-water and oil-in-water emulsions. These emulsions contain bitumen and water and need to be broken, the bitumen is sent for upgrading / refining, while the produced water (separated from the emulsion) is treated and reused as feedwater for the steam generators.

[0005] From a simple practical standpoint, it is highly desirable to separate as much of the oil or other hydrocarbon compounds as possible from the production fluids in oil and gas operations after treatment, before the treated production fluids are reused for more oil and gas production or released into the environment.

[0006] Indeed, before the water can be disposed of or reused, it is necessary to separate the oil and solids from the water in order to comply with sales specifications for the oil and provide acceptable specifications.

[0007] However, the desired oil / hydrocarbon and water separation for oil-in-water or complex emulsions can be difficult by physical processes alone due to the nature of the emulsion. In such situations, demulsifying coagulants and flocculants, e.g., inverse emulsion breakers, can be used to break the emulsion and hasten the agglomeration of oil particles. Inorganic coagulants, either alone or in combination with organic polyelectrolytes, have been used to demulsify production fluids in oil and gas operations.

[0008] Typically, the separation system will have equipment for treating the production fluid to facilitate further separation of the oil droplets from the water. This equipment includes hydrocyclones, flotation tanks, filtration units, and centrifuges. The performance of these devices can be significantly improved using chemical inverse emulsion breakers. Inverse emulsion breakers are interchangeably called deoiling agents (by removing oil) or water clarifiers (by improving water quality).

[0009] Additionally, emulsion droplets not removed by the primary separation system will be significantly stabilized from further coalescence by two mechanisms. The first is mutual charge repulsion of the emulsion droplets. When the fluid is processed, pressure reduction increases the pH of the water, resulting in the deprotonation of the naturally occurring fatty and naphthenic acids present in the crude oil. These salts provide a negative charge to the emulsion surface, repelling other oil droplets that would coalesce upon interaction.

[0010] The second is organic and / or inorganic solids adsorbed at the emulsion oil / water interface, effectively sealing the interface from exposure to other emulsion droplets and impeding the coalescence mechanism. If the emulsion droplets are small enough, Brownian motion keeps the emulsion stable indefinitely. For example, in high total dissolved solids (TDS) brines, calcium soaps of fatty acids / naphthenic acids form, creating a solid phase at the water interface and further slowing coalescence.

[0011] Effective de-oiling can be achieved using polyelectrolytes that promote the coalescence of emulsion droplets into larger aggregates, which are then more easily acted upon by physical separation equipment in water treatment processes. Polyelectrolytes neutralize the repulsive charges that develop on the emulsion droplets and, if of sufficient size, can also bridge between the droplets, causing them to aggregate together into aggregated groups where proximity can cause coalescence. Inverse emulsion breakers are designed to function in high salinity brines that are common in production fluids.

[0012] For a more effective and efficient oil / hydrocarbon separation process, various chemicals have been invented or investigated as inverse emulsion breakers. Tried chemicals include various cationic polymers or molecules. However, there is still a need for better inverse emulsion breakers as the existing ones are insufficient.

[0013] Quaternary ammonium compounds have been used for many years as inverse emulsion breakers (REBs). Quaternary ammonium compounds belong to an important subcategory of surfactants because they contain unique properties. The main difference between quaternary ammonium compounds and other surfactants is their unique structure. Quaternary ammonium compounds consist mainly of two moieties, a hydrophobic group, e.g., a long alkyl group, and a quaternary ammonium base. The unique positive charge of ammonium plays an important role, e.g., electrostatic interactions between the surfactant and the surface or on the surface of the emulsion droplets. However, the quaternary ammonium compounds used for such purposes are often bisquaternary species or species quaternized with benzyl chloride, which are known to be very harmful. In addition, there are government regulations for the release of any water containing a single quaternary compound into the environment. Summary of the Invention [Problem to be solved by the invention]

[0014] Therefore, there is a continuing need for different quaternary ammonium compounds that are better and safer inverse emulsion breakers.

[0015] It is therefore an objective to develop new inverse emulsion breakers with improved properties having improved oil / hydrocarbon and water separation properties.

[0016] A further object of the present disclosure is to develop methods for making novel compounds efficiently and effectively.

[0017] A further object of the present disclosure is to use the novel compounds in articles, products, and / or compositions.

[0018] It is also an object of the present disclosure to develop new inverse emulsion breakers with improved oil / hydrocarbon and water separation properties.

[0019] A further object of the present disclosure is to develop methods and corresponding inverse emulsion breaking compositions for more efficient and effective separation of oil / hydrocarbons and water in production fluids in oil and gas operations.

[0020] These and other objects, advantages, and features of the present disclosure will become apparent from the following specification, taken in conjunction with the claims set forth herein. [Means for solving the problem]

[0021] Disclosed herein are novel compounds, methods of making the disclosed compounds, and articles, products, or compositions comprising the disclosed compounds. More specifically, disclosed herein are multiply charged cationic or anionic compounds that contain multiple positive or negative charges within a single molecule of various molecular sizes and are derived from water-soluble polyamines.

[0022] Also disclosed herein are methods of using one or more multiply charged cationic or anionic compounds as inverse emulsion breakers in production fluids in oil and gas operations. More specifically, the disclosed methods and compositions for breaking oil-in-water or multiple emulsions in production fluids use one or more multiply charged cationic anionic compounds derived from polyamines.

[0023] The exemplary multiply charged cationic compounds disclosed herein exhibit superior performance to conventional single quaternary ammonium compounds for breaking inverse emulsions in production fluids in oil and gas operations. The exemplary multiply charged cationic compounds disclosed herein also exhibit improved performance when they are used as coagulants, water clarifiers, corrosion inhibitors, clay stabilizers, antimicrobial agents in aqueous systems or other applications. Thus, the disclosed inverse emulsion breaking compositions or methods have the advantage of not only breaking inverse emulsions but also serving other purposes, leading to an overall reduction in chemical usage, cost, and operational complexity.

[0024] In one aspect, provided herein are compounds derived from an aza-Michael addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) bearing an ionizable group according to one of the following formulas: [ka] In the formula, X is NH or O, and R 2 But, H, CH 3 or unsubstituted linear or branched C 2 ~C 10 is an alkyl, alkenyl, or alkynyl group; R 2’ But, H, CH 3 or unsubstituted or substituted linear or branched chain C 1 ~C 10 Alkyl, alkenyl, alkynyl groups, -COOH, -CH 2 COOH, Y', or -(CH 2 ) m -Y', m is an integer from 2 to 4, and R 3 is absent or unsubstituted linear or branched chain C 1 ~C 30 is an alkylene group, and Y is -NR 4 R 5 R 6 (+) and Y' is -COOH, -SO 3 H, -PO 3 H, -OSO 3 H, -OPO 3 H, or a salt thereof; R 4 , R 5 , and R 6 became independent, C 1 ~C 10 Disclosed are compounds wherein the alkyl group is an alkyl group, and the compound is a multiply charged cationic compound, having two or more positive charges, or a multiply charged anionic compound, having two or more negative charges.

[0025] In another aspect, provided herein is a method of making a compound or a salt thereof, the method comprising contacting a polyamine with an activated olefin (Michael acceptor) having an ionizable group according to one of the following formulas: [ka] In the formula, X is NH or O, and R 2 But, H, CH 3 or unsubstituted linear or branched C 2 ~C 10 is an alkyl, alkenyl, or alkynyl group; R 2’ But, H, CH 3 or unsubstituted or substituted linear or branched chain C 1 ~C 10 Alkyl, alkenyl, alkynyl groups, -COOH, -CH 2 COOH, Y', or -(CH 2 ) m -Y', m is an integer from 2 to 4, and R 3 is absent or unsubstituted linear or branched chain C 1 ~C 30 is an alkylene group, and Y is -NR 4 R 5 R 6 (+) and Y' is -COOH, -SO 3 H, -PO 3 H, -OSO 3 H, -OPO 3 H, or a salt thereof; R 4 , R 5 , and R 6 became independent, C 1 ~C 10 A method is disclosed in which an alkyl group, a polyamine and an activated olefin undergo an aza-Michael addition reaction, and the compound is a multiply charged cationic compound having two or more positive charges, or a multiply charged anionic compound having two or more negative charges.

[0026] In yet another aspect, provided herein are articles, products, or compositions comprising one or more compounds disclosed herein.

[0027] In yet another aspect, disclosed herein are compositions for breaking up inverse emulsions in production fluids from oil and gas production systems, the inverse emulsion breaking compositions comprising one or more of the compounds disclosed herein and one or more additional inverse emulsion breaking composition agents. In some embodiments, the inverse emulsion compositions disclosed herein break oil-in-water emulsions in the production fluids.

[0028] In another aspect, disclosed herein is a method of breaking up an inverse emulsion in a production fluid from an oil and gas production system, the method comprising contacting a production fluid of the oil and gas production system with an inverse emulsion breaker (REB) composition to generate a treated production fluid, the inverse emulsion breaking composition comprising one or more of a compound or a salt thereof and one or more additional inverse emulsion breaking composition agents. In some embodiments, the inverse emulsion compositions disclosed herein break oil-in-water emulsions in the production fluid.

[0029] The above summary is illustrative only and is not intended to be limiting in any way. In addition to the above exemplary aspects, embodiments, and features, further aspects, embodiments, and features of the present technology will become apparent to those skilled in the art from the following drawings and detailed description, which show and describe exemplary embodiments of the present technology. Thus, the drawings and detailed description should also be regarded as illustrative in nature and not limiting in any way. [Brief description of the drawings]

[0030] [Figure 1] FIG. 1 shows an exemplary general reaction scheme for producing multiply charged cationic compounds by aza-Michael addition reaction between linear polyamines and activated olefins containing cationic groups (α,β-unsaturated carbonyl compounds). [Diagram 2]FIG. 1 shows an exemplary general reaction scheme for producing multiply charged cationic compounds by aza-Michael addition reaction between branched polyamines and activated olefins containing cationic groups (α,β-unsaturated carbonyl compounds).

[0031] Various embodiments of the present disclosure will now be described in detail with reference to the drawings, in which like reference numerals represent like components throughout the several views. Reference to various embodiments does not limit the scope of the present disclosure. The figures presented herein are presented for illustrative purposes of the present disclosure, not as limitations on the various embodiments according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] In the following detailed description, reference may be made to the accompanying drawings, schemes, and structures that form a part of this specification. In the drawings, like symbols typically identify like elements unless the context dictates otherwise. The exemplary embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein.

[0033] Various embodiments are described below. It should be noted that the specific embodiments are not intended as exhaustive descriptions or as limitations to the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be practiced in any other embodiment(s).

[0034] Disclosed herein are methods and compositions for breaking inverse emulsions in production fluids from oil and gas operations. More specifically, one or more multiply charged cationic or anionic compounds are used in an inverse emulsion breaking composition for breaking inverse or complex emulsions in production fluids in oil and gas operations. These multiply charged cationic or anionic compounds are derived from polyamines via an aza-Michael addition reaction between the polyamines and activated olefins.

[0035] The embodiments of the present disclosure are not limited to any particular composition and method, which may vary and are understood by those skilled in the art. It should be further understood that all terminology used herein is merely for the purpose of describing specific embodiments, and is not intended to be limiting in any manner or scope. For example, as used herein and in the appended claims, the singular forms "a", "an", and "the" may include plural referents unless the content clearly indicates otherwise. Furthermore, all units, prefixes, and symbols may be displayed in their SI recognized form.

[0036] The numerical ranges recited herein include the numbers within the ranges defined. Throughout this disclosure, various aspects of the disclosure are presented in range format. Description in range format is merely for convenience and brevity, and should not be interpreted as an inflexible limitation on the scope of the disclosure. Thus, the description of a range should be considered as specifically disclosing all possible subranges and individual numerical values ​​within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0037] In order to make the present disclosure easier to understand, certain terms are defined first.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art related to the embodiments of the present disclosure.Many methods and materials similar to those described herein, modified or equivalent to those described herein can be used to practice the embodiments of the present disclosure without undue experimentation, and preferred materials and methods are described herein.In describing and claiming the embodiments of the present disclosure, the following technical terms will be used according to the definitions described below.

[0038] The term "about" as used herein refers to variations in numerical quantities that may occur, for example, due to typical measuring and liquid handling procedures used in making concentrates or use solutions in the real world, errors in these procedures, differences in manufacture, source, or purity of ingredients used to make the composition or carry out the method, etc. The term "about" also encompasses amounts that vary due to new equilibrium conditions for a composition obtained from a particular initial mixture. Whether or not modified by the term "about," the claims include the equivalent of the amount.

[0039] As used herein, "substituted" refers to an organic group (e.g., an alkyl group) as defined below in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to a non-hydrogen or non-carbon atom. Substituents also include groups in which one or more carbon atom(s) or hydrogen atom(s) are replaced by one or more bonds, including double or triple bonds, to a heteroatom. Thus, a substituent is substituted with one or more substituents, unless otherwise specified. A substituent may be substituted with 1, 2, 3, 4, 5, or 6 substituents.

[0040] Substituted ring groups include rings and ring systems in which a bond to a hydrogen atom is replaced with a bond to a carbon atom. Thus, substituted cycloalkyl, aryl, heterocyclyl, and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups, as defined herein.

[0041] As used herein, the term "alkyl" or "alkyl group" refers to a saturated hydrocarbon having one or more carbon atoms, and includes straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cycloalkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl substituted alkyl groups (e.g., alkyl substituted cycloalkyl groups and cycloalkyl substituted alkyl groups).

[0042] Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl." As used herein, the term "substituted alkyl" refers to an alkyl group having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, aryloxycarbonyl ... The substituents may include no, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

[0043] In some embodiments, substituted alkyls may include heterocyclic groups. As used herein, the term "heterocyclic group" includes closed ring structures similar to carbocyclic groups in which one or more carbon atoms in the ring is an element other than carbon, such as nitrogen, sulfur, or oxygen. Heterocyclic groups may be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxide, oxirane), thiirane (episulfide), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0044] Alkenyl groups or alkenes are straight, branched, or cyclic alkyl groups having 2 to about 30 carbon atoms and further containing at least one double bond. In some embodiments, alkenyl groups have 2 to about 30 carbon atoms, or typically 2 to 10 carbon atoms. Alkenyl groups can be substituted or unsubstituted. In the case of double bonds in alkenyl groups, the configuration of the double bond can be trans or cis configuration. Alkenyl groups can be substituted in the same manner as alkyl groups.

[0045] Alkenyl groups are straight-chain, branched-chain, or cyclic alkyl groups having from 2 to about 30 carbon atoms and further containing at least one triple bond. In some embodiments, alkynyl groups have from 2 to about 30 carbon atoms, or typically from 2 to 10 carbon atoms. Alkynyl groups can be substituted or unsubstituted. Alkynyl groups can be substituted in the same manner as alkyl or alkenyl groups.

[0046] As used herein, the terms “alkylene,” “cycloalkylene,” “alkynyl,” and “alkenylene,” alone or as part of another substituent, each represent —CH 2 CH 2 CH 2 "-" refers to a divalent radical derived from an alkyl, cycloalkyl, or alkenyl group, as exemplified by -. For alkylene, cycloalkylene, alkynylene, and alkenylene groups, no orientation of the linking group is implied.

[0047] As used herein, the term "ester" refers to an -R 30 COOR 31 R 30 R is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein. 31is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0048] As used herein, the term "amine" (or "amino") refers to a -R 32 NR 33 R 34 R 32 R is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein. 33 and R 34 is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0049] As used herein, the term "amine" also refers to an independent compound. When an amine is a compound, R 32’ NR 33’ R 34’ The compound can be represented by the formula: 32’、 R 33’ and R 34 is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0050] As used herein, the term "alcohol" refers to an -R 35 Refers to the OH group. R 35 is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein.

[0051] As used herein, the term "carboxylic acid" refers to a -R 36 Refers to the COOH group. 36 is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein.

[0052] As used herein, the term "ether" refers to a -R 37 OR 38 R 37 R is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein. 38 is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0053] The term "solvent" as used herein refers to any inorganic or organic solvent. Solvents are useful in the disclosed methods or compositions as reaction solvents or carrier solvents. Suitable solvents include, but are not limited to, oxygenated solvents such as lower alkanols, lower alkyl ethers, glycols, aryl glycol ethers, and lower alkyl glycol ethers. Examples of other solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol, as well as butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycol ethers, mixed ethylene-propylene glycol ethers, ethylene glycol phenyl ether, and propylene glycol phenyl ether. Water is also a solvent. Solvents as used herein can be a single solvent or a mixture of many different solvents.

[0054] Glycol ethers include, but are not limited to, diethylene glycol n-butyl ether, diethylene glycol n-propyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol t-butyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methyl ether acetate, propylene glycol n-butyl ether, propylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, tripropylene glycol methyl ether and tripropylene glycol n-butyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, and the like, or mixtures thereof.

[0055] acid The compositions disclosed herein can include an acid. However, in some embodiments, the compositions disclosed herein do not include an acid.

[0056] Generally, acid, as used in this disclosure, includes both organic and inorganic acids. Organic acids include, but are not limited to, hydroxyacetic acid (glycolic acid), formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid. Organic acids also include dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid. Combinations of these organic acids may also be used. Inorganic acids include, but are not limited to, mineral acids, such as phosphoric acid, sulfuric acid, sulfamic acid, methylsulfamic acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, and nitric acid. Inorganic acids may be used alone, in combination with other inorganic acid(s), or in combination with one or more organic acids. Acid generators, including, for example, potassium fluoride, sodium fluoride, lithium fluoride, ammonium fluoride, ammonium bifluoride, sodium silicofluoride, and the like, can be used to form a suitable acid.

[0057] Examples of acids that are particularly suitable for the method or composition disclosed herein include inorganic and organic acids.Exemplary inorganic acids include phosphoric acid, phosphonic acid, sulfuric acid, sulfamic acid, methylsulfamic acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, and nitric acid.Exemplary organic acids include hydroxyacetic acid (glycolic acid), citric acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid.Organic dicarboxylic acids such as oxalic acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid can also be used.

[0058] Percarboxylic Acid and Peroxycarboxylic Acid Compositions Peroxycarboxylic acids (i.e., peracids) or peroxycarboxylic acid compositions may be included in the articles, products, or compositions disclosed herein. As used herein, the term "peracid" may also be referred to as "percarboxylic acid," "peroxycarboxylic acid," or "peroxy acid." Sulfoperoxycarboxylic acids, sulfonated peracids, and sulfonated peroxycarboxylic acids are also included within the terms "peroxycarboxylic acid" and "peracid" as used herein. As one skilled in the art will appreciate, peracid refers to an acid in which the hydrogen of the hydroxyl group in a carboxylic acid is replaced with a hydroxy group. Oxidized peracids may also be referred to herein as peroxycarboxylic acids.

[0059] Peracids have the formula R--(COOOH) n where R is hydrogen, an alkyl, an alkenyl, an alkyne, an acyl, an alicyclic group, an aryl, a heteroaryl, or a heterocyclic group, and n is 1, 2, or 3, and is named by prepending peroxy to the parent acid. Preferably, R comprises a hydrogen, an alkyl, or an alkenyl. The terms "alkyl", "alkenyl", "alkyne", "acyl", "alicyclic group", "aryl", "heteroaryl", and "heterocyclic group" are as defined herein.

[0060] Peroxycarboxylic acid compositions, as used herein, refer to any composition that includes one or more peracids, their corresponding acids, and hydrogen peroxide or other oxidizing agents. Peroxycarboxylic acid compositions can also include stabilizers, fluorescently active tracers or compounds, or other ingredients, as known to those skilled in the art.

[0061] As used herein, the term "mixed" or "mixture" when used with respect to a "percarboxylic acid composition," "percarboxylic acid," "peroxycarboxylic acid composition," or "peroxycarboxylic acid" refers to a composition or mixture that includes two or more percarboxylic acids or peroxycarboxylic acids. Peracids such as peracetic acid and peroctanoic acid may be used. Any combination of these acids may also be used.

[0062] However, in some embodiments, the article, product, or composition does not include a peroxycarboxylic acid or a peroxycarboxylic acid composition.

[0063] Alkaline source or base The compositions disclosed herein may include an alkaline source as a base or an alkaline source. The methods disclosed herein may include using an alkaline source or a base as a catalyst. However, in some embodiments, the compositions or methods disclosed herein do not include a base or an alkaline source.

[0064] The alkaline source, in turn, includes one or more bases or alkaline compounds. In general, an effective amount of the alkaline source should be considered as an amount that provides a use solution of the composition or composition with a pH of at least about 8. When the use solution has a pH of about 8 to about 10, it is considered slightly alkaline, and when the pH is greater than about 12, the solution can be considered caustic.

[0065] The alkali source may include an alkali metal carbonate, an alkali metal hydroxide, an alkali metal silicate, or a mixture thereof. Suitable metal carbonates that may be used include, for example, sodium or potassium carbonate, bicarbonate, sesquicarbonate, or a mixture thereof. Suitable alkali metal hydroxides that may be used include, for example, sodium hydroxide, lithium hydroxide, or potassium hydroxide. Examples of useful alkali metal silicates include sodium or potassium silicate (M of 2.4 to 5:1). 2 O:SiO 2The alkali source may also include a metal borate such as sodium borate or potassium borate.

[0066] The alkaline source may also include ethanolamine, urea sulfate, amines, amine salts, and quaternary ammonium. The simplest cationic amines, amine salts, and quaternary ammonium compounds are depicted generally as follows: [ka] where R represents a long alkyl chain, R', R'', and R''' can be either long alkyl chains or smaller alkyl or aryl groups, or hydrogen, and X represents an anion.

[0067] In some embodiments, the composition does not include an alkaline source or a base.

[0068] Polyamines Polyamines are NH 2 -[R 10’ ] n -NH 2 , (RNH) n -RNH 2 , H 2 N-(RNH) n -RNH 2 , or H 2 N-(RN(R')) n -RNH 2 The compound may have the general formula, but is limited to: 10’ is linear or branched, unsubstituted or substituted C 2 ~C 10 alkylene groups, or combinations thereof, and R is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 alkylene groups, or combinations thereof, where R' is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 Alkyl group, RNH 2 , R.N.H.R.N.H. 2 , or RN(RNH 2 ) 2 and n can be from 2 to 1,000,000. The monomers in the polyamine, such as R or R' groups, can be the same or different. In this disclosure, polyamine refers to both small molecule polyamines, when n is from 1 to 9, and polymeric polyamines, when n is from 10 to 1,000,000.

[0069] Small molecule polyamines include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and tris(2-aminoethyl)amine.

[0070] Other possible polyamines include the JEFFAMINE® monoamines, diamines, and triamines by Huntsman. These highly versatile products contain primary amino groups attached to the ends of a polyether backbone, usually based on propylene oxide (PO), ethylene oxide (EO), or a mixture of both oxides. The JEFFAMINE® amines include a family of polyetheramines consisting of monoamines, diamines, and triamines based on a core polyether backbone structure. The JEFFAMINE® amines also include high conversion and polytetramethylene glycol (PTMEG) based polyetheramines. These JEFFAMINE® amines range in average molecular weight (M) from about 130 to about 4,000. w ).

[0071] The polyamines used in the present disclosure may be polyamine derivatives or modified polyamines, in which one or more, but not all, of the NH protons in the polyamine are unsubstituted or replaced by a substituent. For example, alkyl polyamines containing one or more alkyl groups attached to the nitrogen atom can be used to produce the multiply charged cationic or anionic compounds disclosed herein. In these PEI derivatives, the primary NH 2 Or only some of the secondary NH protons are replaced by other aprotic groups, and the remaining NH 2 Alternatively, the NH proton can still react with a Michael acceptor, such as an activated olefin containing a hydrophilic (ionic) group, via an aza-Michael addition reaction.

[0072] One class of polymeric polyamines includes polyethyleneimine (PEI) and its derivatives. Polyethyleneimine (PEI) or polyaziridine is a CH 2 CH 2 It is a polymer having repeating units of NH, 2 (CH 2 CH 2 NH) n -CH 2 CH 2 NH 2where n is 2 to 10. 5 The repeating monomer in PEI has a molecular weight of 43.07 and a nitrogen to carbon ratio of 1:2.

[0073] PEI and their derivatives can be linear, branched, or dendritic. Linear polyethyleneimine contains all secondary amines, in contrast to branched PEI, which contains primary, secondary, and tertiary amino groups. Fully branched dendritic forms also exist and contain primary and tertiary amino groups. Diagrams for unmodified linear, branched, and dendritic PEI are shown below. [ka]

[0074] PEI derivatives are usually obtained by replacing the proton(s) on the nitrogen atom with different groups. One such PEI derivative is ethoxylated and propoxylated PEI, where polyethyleneimine is derivatized with ethylene oxide (EO) and / or propylene oxide (PO) side chains. Ethoxylation of PEI can increase the solubility of PEI.

[0075] PEI is produced on an industrial scale. Various commercially available polyethyleneimines are available, including, for example, those sold under the trade name Lupasol® (BASF), such as Lupasol® FG, Lupasol® G, Lupasol® PR8515, Lupasol® WF, Lupasol® G20 / 35 / 100, Lupasol® HF, Lupasol® P, Lupasol® PS, Lupasol® PO100, Lupasol® PN50 / 60, and Lupasol® SK. These PEIs have average molecular weights (M) of about 800, about 1,300, about 2,000, about 5,000, about 25,000, about 1,300 / 2,000 / 5,000, about 25,000, about 750,000, about 750,000, about 1,000,000, and about 2,000,000, respectively. w ).

[0076] Two commonly used averages for the molecular weight of polymers are the number average molecular weight (M n ) and weight average molecular weight (M w ) The polydispersity index (D) represents the molecular weight distribution of a polymer. Mn = (Σn i M i ) / Σn i , M w =(Σn i M i 2 ) / Σn i M i , and D=M w / M n where index number i represents the number of different molecular weights present in the sample, and n i is the number of moles and M i For polymers, M n and M. w For example, PEI compounds have an M of about 10,000 by GPC. n and about 25,000 M in LS. w may have the following structure:

[0077] Light scattering (LS) is the M w It can be used to measure the molecular weight of a sample or product. Another simple method to measure the molecular weight of a sample or product is gel permeation chromatography (GPC). GPC is an analytical technique that separates molecules in a polymer by size, providing a molecular weight distribution of the material. Sometimes GPC is also known as size exclusion chromatography (SEC). This technique measures their M n and M. w It is often used for the analysis of polymers with respect to both

[0078] These commercially available and exemplary polyethyleneimines are water soluble and are available as anhydrous and / or modified polyethyleneimines provided in aqueous solution or methoxypropanol (for Lupasol® PO100).

[0079] Suitable polyethyleneimines useful in the present disclosure may contain a mixture of primary, secondary, and tertiary amine substituents, or a mixture of different average molecular weights. The mixture of primary, secondary, and tertiary amine substituents may be in any ratio, including, for example, in a ratio of about 1:1:1 to about 1:2:1, branching every 3 to 3.5 nitrogen atoms along the chain segment. Alternatively, suitable polyethyleneimine compounds may be predominantly one of primary, secondary, or tertiary amine substituents.

[0080] The polyamines that can be used to make the multiply charged cationic or anionic compounds disclosed herein can have a variety of their average molecular weights. Different multiply charged cationic or anionic compounds with their characteristic average molecular weights can be produced by selecting different starting small molecule polyamines, polymeric PEI, or mixtures thereof. By controlling the size of the polyamine or PEI, as well as the degree of modification with activated olefins containing ionic groups, multiply charged cationic or anionic compounds with similar average molecular weights and multiple cationic or anionic charges can be produced. Due to this feature, different multiply charged cationic or anionic compounds can be produced and used for a wider range of applications than using unmodified polyamines or PEI.

[0081] Specifically, polyamines that can be used to make the multiply charged cationic or anionic compounds disclosed herein include those having a molecular weight of about 60-200, about 100-400, about 100-600, about 600-5,000, about 600-800, about 800-2,000, about 800-5,000, about 100-2,000,000, about 100-25,000, about 600-25,000, about 800-25,000, about 600-750,000, about 800-750,000, about 25,000, The average molecular weight (M) of 0 to 750,000, about 750,000 to 2,000,000, about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 1,000, about 1,500, about 2,000, about 3,000, about 5,000, about 8,000, about 10,000, about 15,000, about 20,000, about 50,000, about 100,000, about 250,000, about 500,000, about 1,000,000, about 2,000,000, or any value therebetween. w ).

[0082] Aza-Michael addition reaction between polyamines and activated olefins The multiply charged cationic or anionic compounds disclosed herein are derived from the aza-Michael addition reaction between polyamines and activated olefins containing hydrophilic ionic groups.

[0083] Aliphatic amine groups can undergo aza-Michael addition reactions when contacted with an unsaturated hydrocarbon moiety (e.g., a carbon-carbon double bond) that is in close proximity to an electron-withdrawing group such as a carbonyl, cyano, or nitro group. Specifically, a Michael addition is a reaction between a nucleophile and an activated olefin and an alkyne functionality, where the nucleophile adds across a carbon-carbon multiple bond that is adjacent to an electron-withdrawing group such as a carbonyl group and a resonance-stabilized activating group. The Michael addition nucleophile is known as a "Michael donor," the activated electrophilic olefin is known as a "Michael acceptor," and the reaction product of the two components is known as a "Michael adduct." Examples of Michael donors include, but are not limited to, amines, thiols, phosphines, carbanions, and alkoxides. Examples of Michael acceptors include, but are not limited to, acrylates, alkyl methacrylates, acrylonitrile, acrylamides, maleimides, cyanoacrylates, and vinyl sulfones, vinyl ketones, nitroethylenes, α,β-unsaturated aldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridines, azo compounds, beta-ketoacetylenes, and acetylenic esters.

[0084] As used herein, "activated olefin" refers to a substituted alkene in which at least one of the double-bonded carbons bears a conjugated electron-withdrawing group. Examples of activated olefins include α,β-unsaturated carbonyl compounds (CH 2 =CHCO-NH-CH 3 , alkyl-CH=CH-CO-alkyl, CH 2 =CH 2 C(O)-O-CH 3 ), C.H. 2 =CH-COOH, CH 2 =CH(CH 3 )-COOH, CH 2 =CH-SO 3H, etc., but are not limited to these.

[0085] It has been found that the aza-Michael addition reaction can be used to synthesize the disclosed compounds in high yields (greater than 98%), sometimes within about 24 hours, without the use of high temperatures in excess of 200° C. and pressures greater than standard atmospheric pressure.

[0086] The aza-Michael addition reaction can be catalyzed by a strong acid or a strong base. In some cases, some ionic liquids can function as both a reaction medium and a catalyst. A preferred catalyst for the aza-Michael addition reaction to synthesize the disclosed compounds is a base. Exemplary base catalysts can be hydroxides and amines. The reaction to synthesize the disclosed compounds uses polyamines that usually contain polyamine groups, so the primary polyamine group itself can function as a catalyst for the reaction. In such embodiments, no additional catalyst is required or is optional. Other preferred catalysts include amidine and guanidine bases.

[0087] The use of a solvent and / or diluent for the reaction is optional. When used, various non-acidic solvents are suitable, such as, for example, water, ethers (e.g., tetrahydrofuran (THF)), aromatic hydrocarbons (e.g., toluene and xylene), alcohols (e.g., n-butanol), esters (e.g., ethyl 3-ethoxypropionate), etc. Since the synthetic process is relatively insensitive to solvents, a variety of solvents can be used for the reaction. When a solvent (or diluent) is used, the loading level can range from about 10% by weight up to about 80% by weight or more. The solvent fill level can be about 0 wt%, about 1 wt% to about 10 wt%, about 10 wt% to about 20 wt%, about 20 wt% to about 30 wt%, about 30 wt% to about 40 wt%, about 40 wt% to about 50 wt%, about 50 wt% to about 60 wt%, about 60 wt% to about 70 wt%, about 70 wt% to about 80 wt%, about 1 wt% to about 20 wt%, about 20 wt% to about 40 wt%, about 40 wt% to about 60 wt%, about 60 wt% to about 80 wt%, about 40 wt% to about 70 wt%, at least about 5 wt%, about 15 wt%, about 25 wt%, about 35 wt%, about 45 wt%, about 55 wt%, about 65 wt%, about 75 wt%, or any value therebetween in the final reaction mixture.

[0088] In general, the reaction can be carried out at a range of temperatures. The reaction temperature can range from about 0°C to about 150°C, more preferably from about 50°C to about 80°C. The temperature for contacting the polyamine with the activated olefin can range from about 10°C to about 140°C, about 20°C to about 130°C, about 30°C to about 120°C, about 40°C to about 110°C, about 50°C to about 100°C, about 60°C to about 90°C, about 70°C to about 80°C, about 0°C to about 20°C, about 20°C to about 40°C, about 40°C to about 60°C, about 60°C to about 80°C, about 80°C to about 100°C, about 100°C to about 120°C, about 120°C to about 150°C, about 150°C to about 160°C, about 170°C to about 180°C, about 180°C to about 20°C, about 190°C to about 30°C, about 20°C to about 30°C, about 20°C to about 40°C, about 40°C to about 60°C, about 60°C to about 80°C, about 80°C to about 100°C, about 100°C to about 120°C, about 120°C to about 150°C, about 20°C to about 30°C, about 20°C to about 40°C, about 20°C to about 50°C, about 20°C to about 50°C, about 20°C to about 50°C, about 2 ℃ The reaction temperature may be about 150° C., about 5° C., about 25° C., about 45° C., about 65° C., about 85° C., about 105° C., about 125° C., about 145° C., or any value therebetween. The reaction temperature may be about the same from the start of the reaction to the end of the reaction, or may be changed from one temperature to another as the reaction continues.

[0089] Reaction times for the synthesis of the compounds disclosed herein can vary widely depending on such factors as reaction temperature, availability and amount of catalyst, presence or absence of diluent (solvent), etc. Preferred reaction times can be about 0.5 hours to about 48 hours, about 1 hour to about 40 hours, about 2 hours to about 38 hours, about 4 hours to about 36 hours, 6 hours to about 34 hours, about 8 hours to about 32 hours, about 10 hours to about 30 hours, about 12 hours to about 28 hours, about 14 hours to about 26 hours, about 16 hours to about 24 hours, about 18 hours to about 20 hours, about 1 hour to 8 hours, 8 hours to 16 hours, 8 hours to about 24 hours, about 2 hours, about 4 hours, about 6 hours, about 8 hours, about 10 hours, about 14 hours, about 16 hours, about 18 hours, about 24 hours, about 30 hours, about 36 hours, or any value therebetween.

[0090] The reaction for the synthesis of the compounds disclosed herein can be completed when one mole of polyamine and two or more moles of activated olefin are mixed together at the above temperatures for a sufficient period of time.

[0091] The progress of the reaction can typically be monitored for monomer consumption by ESI-MS and / or NMR spectroscopy. The reaction products can be purified or separated by HPLC or other methods known to those skilled in the art. For reactions that have proceeded to completion, the products formed can be separated by removal of the solvent or by precipitation in a non-polar solvent that was the opposite of the reaction medium. For reactions in water, the products formed precipitate from the aqueous reaction mixture. Higher pressures can accelerate the reaction. In some embodiments, when the reaction is carried out at room temperature, the reaction can have a product yield of greater than 98% in some embodiments within about 16 hours.

[0092] Other reverse emulsion breaking agents in the reverse emulsion breaking composition In addition to the polyamine-derived multiply charged cationic or anionic compounds described herein, the reverse emulsion breaking compositions of the present disclosure include one or more additional reverse emulsion breaking agents.

[0093] Additional reverse emulsion breaking compositions in the disclosed reverse emulsion breaking compositions include acids, carriers, dispersants, biocides, inorganic salts, organic salts, emulsifiers, additional reverse emulsion breakers, corrosion inhibitors, antioxidants, polymer degradation inhibitors, osmotic control agents, foaming agents, defoamers, fracturing proppants, glass particulates, sand, fracturing proppant / sand control agents, H 2 S, CO 2 and / or O 2 These may include, but are not limited to, sequestrants for the composition, gelling agents, lubricants, as well as friction reducers, salts, or mixtures thereof.

[0094] Additional reverse emulsion breaking agents in the disclosed REB compositions can also include, but are not limited to, organic sulfur compounds, demulsifiers, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, water clarifiers, emulsion breakers, reverse emulsion breakers, gas hydrate inhibitors, pH adjusters, surfactants, or combinations thereof.

[0095] Additionally, the additional reverse emulsion breaking composition agents can be sequestering agents, solubilizing agents, lubricants, buffering agents, detergents, rinse aids, preservatives, binders, thickeners or other viscosity modifiers, processing aids, carriers, water conditioners, or foam generators, threshold agents or systems, aesthetic enhancers (e.g., dyes, odorants, fragrances), or other additives suitable for combination with the reverse emulsion breakers, or mixtures thereof.

[0096] The additional reverse emulsion breaking components in the REB composition will vary depending on the particular reverse emulsion breaking composition being made and its intended use as would be understood by one of ordinary skill in the art.

[0097] Alternatively, the reverse emulsion breaking composition does not contain or is free of one or more of the additional reverse emulsion breaking composition agents.

[0098] When one or more additional reverse emulsion breaking composition agents are used to break up an inverse emulsion or a multiple emulsion, they can be formulated together with the polyamine-derived multiply charged cationic or anionic compounds as described herein in the same reverse emulsion breaking composition. Alternatively, some or all of the additional reverse emulsion breaking composition agents can be formulated in one or more different formulations and provided to the production fluid. In other words, the additional reverse emulsion breaking composition agents can be provided independently, simultaneously, or sequentially into the production fluid.

[0099] Biocides and Carriers In some embodiments, the reverse emulsion breaking compositions disclosed herein further comprise a biocide. In some embodiments, the reverse emulsion breaking compositions disclosed herein further comprise a carrier. In some embodiments, the reverse emulsion breaking compositions disclosed herein further comprise a biocide and a carrier. In some embodiments, the methods or reverse emulsion breaking compositions disclosed herein may consist of one or more multiply charged cationic or anionic compounds disclosed herein and a carrier. In some embodiments, the reverse emulsion breaking compositions disclosed herein consist of one or more multiply charged cationic or anionic compounds disclosed herein, a carrier, and a biocide.

[0100] Biocides suitable for use can be oxidizing or non-oxidizing biocides. Oxidizing biocides include, but are not limited to, bleach, chlorine, bromine, chlorine dioxide, peroxycarboxylic acids, peroxycarboxylic acids, and materials capable of releasing chlorine, bromine, or peroxide. Non-oxidizing biocides include glutaraldehyde, isothiazolinone, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3 diol, 1-bromo-1-(bromomethyl)-1,3-propanedicarbonitrile, tetrachloroisophthalonitrile, alkyldimethylbenzylammonium chloride, dimethyldialkylammonium chloride, didecyldimethylammonium chloride, poly(oxyethylene(dimethyliminio)ethylene). (dimethyliminio)ethylene dichloride, methylene bisthiocyanate, 2-decylthioethanamine, tetrakis hydroxymethylphosphonium sulfate, dithiocarbamate, cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-1-ethanol, 2-(2-bromo-2-nitroethenyl)furan, β-bromo-β-nitrostyrene, β-nitrostyrene, β-nitrovinylfuran, 2-bromo-2-bromomethylglutaronitrile, bis (Trichloromethyl)sulfone, S-(2-hydroxypropyl)thiomethanesulfonate, tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione, 2-(thiocyanomethylthio)benzothiazole, 2-bromo-4'-hydroxyacetophenone, 1,4-bis(bromoacetoxy)-2-butene, bis(tributyltin)oxide, 2-(tert-butylamino)-4-chloro-6-(ethylamino)-s-triazine, dodecylguanidine Acetate, dodecylguanidine hydrochloride, cocoalkyldimethylamine oxide, n-cocoalkyltrimethylenediamine, tetra-alkylphosphonium chloride, 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 2-methyl-4-isothiazolin-3-one.

[0101] Suitable non-oxidizing biocides also 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., isothiazolones, carbamates, and metronidazole), and quaternary phosphonium salts (e.g., tetrakis(hydroxymethyl)-phosphonium sulfate (THPS)).

[0102] Suitable oxidizing biocides include, for example, sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorinated hydantoins, stabilized sodium hypobromite, activated sodium bromide, brominated hydantoins, chlorine dioxide, ozone, peroxycarvone, peroxycarvone compositions, and peroxides.

[0103] The composition can include about 0.1% to about 10%, about 0.5% to about 5%, or about 0.5% to about 4% by weight of a biocide based on the total weight of the composition.

[0104] The carrier in the disclosed inverse emulsion breaking compositions can be water, an organic solvent, or a combination of water and an organic solvent. The organic solvent can be an alcohol, a hydrocarbon, a ketone, an ether, an alkylene glycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, or a combination thereof. Examples of suitable organic solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, methylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutyl ketone, diethyl ether, propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, or combinations thereof.

[0105] The composition may comprise from about 1% by weight to about 80% by weight, from about 5% by weight to about 50% by weight, from about 5% by weight to about 45% by weight, from about 5% by weight to about 30% by weight, from about 5% by weight to about 25% by weight, from about 5% by weight to about 20% by weight, from about 5% by weight to about 15% by weight, from about 5% by weight to about 10% by weight, from about 10% by weight to about 35% by weight, from about 10% by weight to about 25% by weight, or from about 10% by weight to about 35% by weight, based on the total weight of the composition.

[0106] Corrosion Inhibitors In some embodiments, the reverse emulsion breaking compositions disclosed herein further comprise a corrosion inhibitor. In some other embodiments, the reverse emulsion breaking compositions disclosed herein further comprise a corrosion inhibitor and a carrier. In some other embodiments, the reverse emulsion breaking compositions disclosed herein further comprise a corrosion inhibitor, a biocide, and a carrier. In some embodiments, the reverse emulsion breaking compositions disclosed herein may consist of one or more multiply charged cationic or anionic compounds disclosed herein, one or more corrosion inhibitors, and a carrier. In some embodiments, the reverse emulsion breaking compositions disclosed herein consist of one or more multiply charged cationic or anionic compounds disclosed herein, a carrier, a corrosion inhibitor, and a biocide.

[0107] The inverse emulsion breaking composition can include from about 0.1% to about 20%, from about 0.1% to about 10%, or from 0.1 to about 5% by weight of one or more corrosion inhibitors, based on the total weight of the composition. The compositions of the present disclosure can include from about 0% to about 10% by weight of one or more corrosion inhibitors, based on the total weight of the composition. The composition can comprise about 1.0 wt%, about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, about 3.0 wt%, about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt%, about 5.5 wt%, about 6.0 wt%, about 6.5 wt%, about 7.0 wt%, about 7.5 wt%, about 8.0 wt%, about 8.5 wt%, about 9.0 wt%, about 9.5 wt%, about 10.0 wt%, about 10.5 wt%, about 11.0 wt%, about 11.5 wt%, about 12.0 wt%, about 12.5 wt%, about 13.0 wt%, about 13.5 wt%, about 14.0 wt%, about 14.5 wt%, or about 15.0 wt% of one or more corrosion inhibitors based on the total weight of the composition. Each production fluid may have its own requirements for the use of corrosion inhibitors, and the weight percentage of one or more corrosion inhibitors in the composition may vary depending on the production fluid in which it is used.

[0108] Corrosion inhibitors are required to reduce corrosion of metals in contact with production fluids. Corrosion inhibitors for multi-metal protection are typically triazoles, such as, but not limited to, benzotriazoles, halogenated triazoles, and nitro-substituted azoles.

[0109] The one or more corrosion inhibitors may be an imidazoline compound, a quaternary ammonium compound, a pyridinium compound, or a combination thereof.

[0110] One or more of the corrosion inhibitor components may be an imidazoline. The imidazoline may be, for example, an imidazoline derived from a diamine such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), and long chain fatty acid such as tall oil fatty acid (TOFA). The imidazoline may be an imidazoline or imidazoline derivative of formula (1A). Representative imidazoline derivatives include an imidazolinium compound of formula (2A) or a bisquaternized compound of formula (3A).

[0111] The one or more corrosion inhibitors may include an imidazoline of formula (1A): [ka] In the formula, R 10a is C 1 ~C 20 Alkyl group or C 1 ~C 20 is an alkoxyalkyl group, R 11a is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Hydroxyalkyl, or C 1 ~C 6 arylalkyl, R 12a and R 13a are independently hydrogen or C 1 ~C 6 Preferably, the imidazoline is an alkyl group, R 2 , which is an alkyl mixture typical of tall oil fatty acid (TOFA). 10aIncluding R 11a , R 12a , and R 13a are each hydrogen.

[0112] The one or more additional corrosion inhibitors may be an imidazolinium compound of formula (2A): [ka] In the formula, R 10a is C 1 ~C 20 Alkyl group or C 1 ~C 20 is an alkoxyalkyl group, R 11a and R 14a are independently hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Hydroxyalkyl, or C 1 ~C 6 arylalkyl, R 12a and R 13a are independently hydrogen or C 1 ~C 6 is an alkyl group, and X - is an anion of a halide (such as chloride, bromide, iodide), carbonate, sulfonate, phosphate, or organic carboxylic acid (such as acetate). Preferably, the imidazolinium compound comprises 1-benzyl-1-(2-hydroxyethyl)-2-tall oil-2-imidazolinium chloride.

[0113] The one or more additional corrosion inhibitors may be a bisquaternized compound having the formula (3A): [ka] In the formula, R 1a and R 2aare each independently an unsubstituted branched, linear, or cyclic alkyl or alkenyl having 1 to about 29 carbon atoms; a partially or fully oxygenated, sulfurized, and / or phosphorylated branched, linear, or cyclic alkyl or alkenyl having 1 to about 29 carbon atoms; or a combination thereof; R 3a and R 4a are each independently an unsubstituted branched, linear, or cyclic alkylene or alkenylene having 1 to about 29 carbon atoms; a partially or fully oxygenated, sulfurized, and / or phosphorylated branched, linear, or cyclic alkylene or alkenylene having 1 to about 29 carbon atoms; or a combination thereof; L 1 and L 2 are each independently absent, H, -COOH, or -SO 3 H, -PO 3 H, -COOR 5a , -CONH 2 , -CONHR 5a , or --CON(R 5a ) 2 and R 5a are each independently a branched or unbranched alkyl, aryl, alkylaryl, alkylheteroaryl, cycloalkyl, or heteroaryl group having 1 to about 10 carbon atoms; n is 0 or 1; and when n is 0, L 2 is absent or is H, x is 1 to about 10, and y is 1 to about 5. 1a and R 2a are each independently 6 ~C 22 Alkyl, C 8 ~C 20 Alkyl, C 12 ~C 18 Alkyl, C 16 ~C 18 alkyl, or a combination thereof; R 3a and R 4a is C 1 ~C 10 Alkylene, C 2 ~C 8 Alkylene, C2 ~C 6 Alkylene, or C 2 ~C 3 alkylene, n is 0 or 1, x is 2, y is 1, R 3 and R 4 -C 2 H 2 - and L 1 -COOH, -SO 3 H, or -PO 3 H and L 2 does not exist or is H, -COOH, -SO 3 H, or -PO 3 H. For example, R 1a and R 2a can be derived from a mixture of tall oil fatty acids, primarily C 17 H 33 and C 17 H 31 or a mixture of C 16 ~C 18 may be alkyl, R 3a and R 4a -C 2 H 2 - C etc. 2 ~C 3 alkylene, n is 1, and L 2 is -COOH or n is 0 and L 2 is absent or is H, x is 2, y is 1, and R 3a and R 4a -C 2 H 2 - and L 1 is -COOH.

[0114] It should be understood that the number of carbon atoms specified for each group in formula (3A) refers to the main chain of carbon atoms and does not include carbon atoms that may be contributed by substituents.

[0115] The one or more corrosion inhibitors may be a bisquaternized imidazoline compound having the formula (3A), where R 1a and R 2a are each independently6 ~C 22 Alkyl, C 8 ~C 20 Alkyl, C 12 ~C 18 Alkyl or C 16 ~C 18 alkyl, or a combination thereof; R 4a is C 1 ~C 10 Alkylene, C 2 ~C 8 Alkylene, C 2 ~C 6 Alkylene, or C 2 ~C 3 alkylene, x is 2, y is 1, n is 0, and L 1 -COOH, -SO 3 H, or -PO 3 H and L 2 is absent or is H. Preferably, the bisquaternized compound has the formula (3A), where R 1a and R 2a are each independently 16 ~C 18 is alkyl, R 4a -C 2 H 2 -, x is 2, y is 1, n is 0, and L 1 -COOH, -SO 3 H, or -PO 3 H and L 2 is absent or H.

[0116] The one or more additional corrosion inhibitors may be a quaternary ammonium compound of formula (4A): [ka] In the formula, R 1a , R 2a , and R 3a is independently 1 ~C 20 is alkyl, R 4a is methyl or benzyl, and X -is a halide or a methosulfate.

[0117] Suitable alkyl, hydroxyalkyl, alkylaryl, arylalkyl, or arylamine quaternary salts include those of the formula [N + R 5a R 6a R 7a R 8a ][X - and alkylaryl, arylalkyl, and arylamine quaternary salts of the formula: 5a , R 6a , R 7a , and R 8a contains 1 to 18 carbon atoms and X is Cl, Br, or I. For quaternary salts, R 5a , R 6a , R 7a , and R 8a are each independently an alkyl group (e.g., C 1 ~C 18 alkyl), hydroxyalkyl (e.g., C 1 ~C 18 The monocyclic or polycyclic aromatic amine salts with alkyl or alkylaryl halides can be of the formula [N + R 5a R 6a R 7a R 8a ][X - wherein R 5a , R 6a , R 7a , and R 8a contains 1-18 carbon atoms and at least one aryl group, and X is Cl, Br, or I.

[0118] Suitable quaternary ammonium salts include, but are not limited to, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetrahexylammonium salts, tetraoctylammonium salts, benzyltrimethylammonium salts, benzyltriethylammonium salts, phenyltrimethylammonium salts, phenyltriethylammonium salts, cetylbenzyldimethylammonium salts, hexadecyltrimethylammonium salts, dimethylalkylbenzyl quaternary ammonium salts, monomethyldialkylbenzyl quaternary ammonium salts, or trialkylbenzyl quaternary ammonium salts, wherein the alkyl group has about 6 to about 24 carbon atoms, about 10 to about 18 carbon atoms, or about 12 to about 16 carbon atoms. The quaternary ammonium salt can be a benzyltrialkyl quaternary ammonium salt, a benzyltriethanolamine quaternary ammonium salt, or a benzyldimethylaminoethanolamine quaternary ammonium salt.

[0119] The one or more corrosion inhibitors may be a pyridinium salt, such as that represented by formula (5A): [ka] In the formula, R 9a is an alkyl group, an aryl group, or an arylalkyl group, the alkyl group having from 1 to about 18 carbon atoms; X - is a halide, such as chloride, bromide, or iodide. Among these compounds are alkyl pyridinium salts and alkyl pyridinium benzyl quaternaries. Exemplary compounds include methyl pyridinium chloride, ethyl pyridinium chloride, propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridinium chloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzyl pyridinium chloride, and alkyl benzyl pyridinium chloride, preferably where alkyl is C 1 ~C 6It is a hydrocarbyl group. Preferably, the pyridinium compound comprises benzylpyridinium chloride.

[0120] The one or more additional corrosion inhibitors may be a phosphate ester, a monomeric or oligomeric fatty acid, an alkoxylated amine, or a mixture thereof.

[0121] The one or more corrosion inhibitors may be a phosphate ester. Suitable mono-, di-, and tri-alkyl, and alkylaryl phosphate esters of mono-, di-, and triethanolamine, and phosphate esters typically contain from 1 to about 18 carbon atoms. Preferred mono-, di-, and trialkyl phosphate esters, alkylaryl, or arylalkyl phosphate esters include those having a C 3 ~C 18 It is prepared by reacting an aliphatic alcohol with phosphorus pentoxide. The phosphate ester intermediate exchanges its ester group with triethyl phosphate to produce a wider variety of alkyl phosphates.

[0122] Alternatively, the phosphate esters can be made by combining an alkyl diester with a mixture of low molecular weight alkyl alcohols or diols. The low molecular weight alkyl alcohols or diols are preferably C 6 ~C 10 Furthermore, phosphate esters of polyols containing one or more 2-hydroxyethyl groups and their salts, as well as hydroxylamine phosphate esters obtained by reacting polyphosphoric acid or phosphorus pentoxide with hydroxylamines such as diethanolamine or triethanolamine, are preferred.

[0123] The one or more corrosion inhibitors may be monomeric or oligomeric fatty acids. A preferred monomeric or oligomeric fatty acid is C 14 ~C 22Saturated and unsaturated fatty acids, as well as dimer, trimer, and oligomer products obtained by polymerizing one or more of such fatty acids.

[0124] The one or more corrosion inhibitors may be an alkoxylated amine. The alkoxylated amine may be an ethoxylated alkyl amine. The alkoxylated amine may be an ethoxylated tallow amine.

[0125] The disclosed multiply charged cationic or anionic compounds have been found to be effective as corrosion inhibitors.In some embodiments, the REB compositions disclosed herein do not contain corrosion inhibitors.Because the disclosed multiply charged cationic or anionic compounds can be REB agents and corrosion inhibitors, the disclosed REB compositions have the advantage of using less chemicals for oil and gas operations.

[0126] Dispersants In some embodiments, the inverse emulsion breaking compositions disclosed herein can further include a dispersant. The dispersant keeps particulate matter present in the production fluid dispersed so that it does not clump. The composition can include about 0.1% to about 10% by weight, about 0.5% to about 5% by weight, or about 0.5% to about 4% by weight of the dispersant based on the total weight of the composition.

[0127] The dispersants may be acrylic acid polymers, maleic acid polymers, copolymers of acrylic acid and sulfonated monomers, their alkyl esters, or combinations thereof. These polymers may include terpolymers of acrylic acid, acrylamide, and sulfonated monomers. These polymers may also include quaternary polymers of acrylic acid and three other monomers.

[0128] Suitable dispersants include, but are not limited to, aliphatic phosphonic acids having 2 to 50 carbons, such as hydroxyethyl diphosphonic acid, and aminoalkyl phosphonic acids, such as polyaminomethylene phosphonates having 2 to 10 N atoms (e.g., each having at least one methylene phosphonic acid group), examples of the latter being ethylenediaminetetra(methylene phosphonate), diethylenetriaminepenta(methylene phosphonate), and triamine- and tetraamine-polymethylene phosphonates, having 2 to 4 methylene groups between each N atom, with at least two of the numbers of methylene groups in each phosphonate being different. Other suitable dispersants include lignin or derivatives of lignin, such as lignosulfonates, and naphthalene sulfonic acids and derivatives.

[0129] The inverse emulsion breaking composition disclosed herein may further comprise an organic sulfur compound, such as a mercaptoalkyl alcohol, mercaptoacetic acid, thioglycolic acid, 3,3'-dithiodipropionic acid, sodium thiosulfate, thiourea, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, sodium metabisulfite, or a combination thereof. Preferably, the mercaptoalkyl alcohol comprises 2-mercaptoethanol. Such compounds are used as synergists in the composition. The organic sulfur compound may comprise about 0.5% to about 15% by weight of the composition, preferably about 1% to about 10% by weight, more preferably about 1% to about 5% by weight, based on the total weight of the composition. The organosulfur compound can comprise about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15% by weight of the composition.

[0130] The reverse emulsion breaking composition may further comprise a demulsifier. Preferably, the demulsifier comprises an oxyalkylate polymer, such as a polyalkylene glycol. The demulsifier may comprise about 0.1% to about 10%, about 0.5% to about 5%, or about 0.5% to about 4% by weight of the composition based on the total weight of the composition. The demulsifier may comprise about 0.5%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, or about 5% by weight of the composition.

[0131] The inverse emulsion breaking composition can further include an asphaltene inhibitor. The composition can include from about 0.1 wt. % to about 10 wt. %, from about 0.1 wt. % to about 5 wt. %, or from about 0.5 wt. % to about 4 wt. % of the asphaltene inhibitor based on the total weight of the composition. Suitable asphaltene suppressants include, but are not limited to, aliphatic sulfonic acids, alkylarylsulfonic acids, arylsulfonates, 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 / vinylpyrrolidone copolymers, graft polymers of polyolefins with maleic anhydride or vinylimidazole, hyperbranched polyesteramides, polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkyl succinates, sorbitan monooleate, and polyisobutylene succinic anhydride.

[0132] The inverse emulsion breaking composition may further comprise a paraffin suppressor. The composition may comprise about 0.1 wt.% to about 10 wt.%, about 0.1 wt.% to about 5 wt.%, or about 0.5 wt.% to about 4 wt.% of a paraffin suppressor based on the total weight of the composition. Suitable paraffin suppressors 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, naphthalenes, anthracenes, microcrystalline waxes, and / or asphaltenes. Suitable paraffin dispersants include, but are not limited to, dodecylbenzene sulfonates, oxyalkylated alkylphenols, and oxyalkylated alkylphenol resins.

[0133] The inverse emulsion breaking composition may further comprise a scale inhibitor. The composition may comprise about 0.1% to about 20% by weight, about 0.5% to about 10% by weight, or about 1% to about 5% by weight of the scale inhibitor based on the total weight of the composition. Suitable scale inhibitors include, but are not limited to, phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonic acids, polyacrylamides, salts of acrylamidomethylpropanesulfonate / acrylic acid copolymers (AMPS / AA), phosphorylated maleic acid copolymers (PHOS / MA), mono-, bis-, and oligomeric phosphinosuccinic acid (PSO) derivatives, polycarboxylic acids, hydrophobically modified polycarboxylic acids, and salts of polymaleic acid / acrylic acid / acrylamidomethylpropanesulfonate terpolymers (PMA / AA / AMPS).

[0134] The inverse emulsion breaking composition can further include an emulsifier. The composition can include about 0.1% to about 10%, about 0.5% to about 5%, or about 0.5% to about 4% by weight of an emulsifier based on the total weight of the composition. 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 sugars (alkyl-sugar emulsifiers).

[0135] The inverse emulsion breaking composition may further comprise a water clarifier. The composition may comprise about 0.1% to about 10%, about 0.5% to about 5%, or about 0.5% to about 4% by weight of the water clarifier based on the total weight of the composition. 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, and cationic polymers such as diallyldimethylammonium chloride (DADMAC) polymers and / or methylacrylamide [3-(methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) polymers.

[0136] The inverse emulsion breaking composition may further comprise an emulsion breaker. The composition may comprise about 0.1% to about 10%, about 0.5% to about 5%, or about 0.5% to about 4% by weight of the emulsion breaker based on the total weight of the composition. Suitable emulsion breakers include, but are not limited to, dodecylbenzylsulfonic acid (DDBSA), sodium salt of xylenesulfonic acid (NAXSA), epoxidized and propoxylated compounds, anionic, cationic, and nonionic surfactants, and resins such as phenolic and epoxy resins.

[0137] In some embodiments, emulsion breaker (demulsifier) ​​is non-ionic emulsion breaker.Suitable non-ionic emulsion breaker includes, but is not limited to, polyether or oxyalkylate derived from diol, triol and polyol; polyester derived from polyether and diacid or polyacid such as adipic acid, fumaric acid, maleic anhydride or acrylic; para-substituted alkylphenol resin oxyalkylate derived from t-butylphenol, t-amylphenol, nonylphenol or butylnonylphenol; polymeric polyether derived from toluene di-isocyanate, diglycidyl ether of bisphenol-A or acrylic acid; and combination of resin oxyalkylate and polymeric polyol such as maleic acid copolymerized with acrylic acid and then further esterified.

[0138] The inverse emulsion breaking composition may further comprise a hydrogen sulfide scavenger. The composition may comprise about 1% to about 50% by weight, about 1% to about 40% by weight, about 1% to about 30% by weight, about 0.1% to about 10% by weight, about 0.5% to about 5% by weight, or about 0.5% to about 4% by weight of the hydrogen sulfide scavenger based on the total weight of the composition. Suitable additional hydrogen sulfide scavengers include, but are not limited to, oxidizers (e.g., inorganic peroxides such as sodium peroxide or chlorine dioxide), aldehydes (e.g., those having 1 to 10 carbon atoms 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 with aldehydes, and condensation products of alkyl alcohols with aldehydes.

[0139] The inverse emulsion breaking composition can further include a gas hydrate inhibitor. The composition can include about 0.1% to about 25% by weight, about 0.5% to about 20% by weight, about 1% to about 10% by weight, about 0.1% to about 10% by weight, about 0.5% to about 5% by weight, or about 0.5% to about 4% by weight of the gas hydrate inhibitor based on the total weight of the composition. Suitable gas hydrate inhibitors include, but are not limited to, thermodynamic hydrate inhibitors (THI), kinetic hydrate inhibitors (KHI), and agglomeration inhibitors (AA). Suitable thermodynamic hydrate inhibitors include, but are not limited to, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, formate brine (e.g., potassium formate), polyols (such as glucose, sucrose, fructose, maltose, lactose, gluconate, monoethylene glycol, diethylene glycol, triethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, glycerol, diglycerol, triglycerol, and sugar alcohols (e.g., sorbitol, mannitol), etc.), methanol, propanol, ethanol, glycol ethers (such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether), and alkyl or cyclic esters of alcohols (such as ethyl lactate, butyl lactate, methyl ethyl benzoate, etc.).

[0140] The inverse emulsion breaking composition can further include a dynamic hydrate inhibitor, the composition can include from about 0.1% to about 25%, from about 0.5% to about 20%, from about 1% to about 10%, from about 0.1% to about 10%, from about 0.5% to about 5%, or from about 0.5% to about 4% by weight of the dynamic hydrate inhibitor, based on the total weight of the composition. Suitable kinetic hydrate inhibitors and flocculation inhibitors include, but are not limited to, polymers and copolymers, polysaccharides (such as hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), starch, starch derivatives, and xanthan), lactams (such as polyvinyl caprolactam, 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 betaines, alkyl amido betaines, and the like), hydrocarbon-based dispersants (such as lignosulfonates, iminodisuccinates, polyaspartates, and the like), amino acids, and proteins.

[0141] The inverse emulsion breaking composition may further comprise a pH adjuster. The composition may comprise about 0.1% to about 20%, about 0.5% to about 10%, or about 0.5% to about 5% by weight of a pH adjuster based on the total weight of the composition. Suitable pH adjusters 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 adjusters include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium oxide, and magnesium hydroxide.

[0142] The inverse emulsion breaking composition may further comprise a surfactant. The composition may comprise from about 0.1% to about 10%, from about 0.5% to about 5%, or from about 0.5% to about 4% by weight of a surfactant based on the total weight of the composition. Suitable surfactants include, but are not limited to, anionic surfactants and nonionic surfactants. Anionic surfactants include alkylaryl sulfonates, olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylates and alkyl ether carboxylates, and alkyl and ethoxylated alkyl phosphate esters, and mono- and dialkyl sulfosuccinates and sulfosuccinates. Nonionic surfactants include alcohol alkoxylates, alkylphenol alkoxylates, block copolymers of ethylene, propylene, and butylene oxide, alkyl dimethylamine oxides, alkyl bis(2-hydroxyethyl)amine oxides, alkyl amidopropyl dimethylamine oxides, alkyl amidopropyl bis(2-hydroxyethyl)amine oxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitan esters, and polyalkoxylated sorbitan esters, and alkoyl polyethylene glycol esters and diesters. Also included are betaines and sultanes, amphoteric surfactants such as alkyl amphoacetates and amphodiacetates, alkyl amphopropionates and amphodipropionates, and alkyl iminodipropionates.

[0143] The inverse emulsion breaking composition may further comprise one or more additional REB composition agents that provide beneficial properties. For example, the additional agents may be sequestering agents, solubilizers, lubricants, buffering agents, detergents, rinse aids, preservatives, binders, thickeners or other viscosity modifiers, processing aids, carriers, water conditioners, antifoaming or foam generating agents, threshold agents or systems, aesthetic improvers (i.e. dyes, odorants, fragrances), or other additives suitable for formulation with the corrosion inhibitor composition, and mixtures thereof. The additional agents or additives will vary depending on the particular inverse emulsion breaking composition being manufactured, and their intended use will be understood by those skilled in the art.

[0144] Alternatively, the reverse emulsion breaking composition does not contain any additional agents or additives.

[0145] Additionally, reverse emulsion breaking compositions can be formulated into compositions containing the following components as shown in Table 1. These formulations contain the ranges of ingredients listed and can optionally include additional agents. The values ​​in the table below are weight percents. [Table 1] [Table 2]

[0146] In some embodiments, the reverse emulsion breaking compositions or multiply charged cationic compounds disclosed herein can be added to the production fluid so that the reverse emulsion breaking composition in the treated production fluid is in an amount ranging from about 1 ppm to about 1000 ppm. In other embodiments, the amount of inverse emulsion breaking composition or multiply charged cationic or anionic compounds in the treated production fluid may range from about 5 ppm to about 200 ppm, from about 10 ppm to about 150 ppm, from about 10 ppm to about 75 ppm, from about 5 ppm to about 50 ppm, from about 5 ppm to about 40 ppm, from about 5 ppm to about 30 ppm, from about 10 ppm to about 60 ppm, from about 10 ppm to about 50 ppm, from about 10 ppm to about 40 ppm, from about 10 ppm to about 75 ppm, from about 20 ppm to about 60 ppm, from about 20 ppm to about 50 ppm, from about 20 ppm to about 40 ppm, or from about 20 ppm to about 30 ppm. In some embodiments, the reverse emulsion breaking composition or multiply charged cationic or anionic compounds can be added to the production fluid so that the reverse emulsion breaking composition or multiply charged cationic or anionic compounds have a concentration in the treated production fluid of from about 10 ppm to about 200 ppm, from about 10 ppm to about 150 ppm, from about 10 ppm to about 100 ppm, or from about 10 ppm to about 75 ppm.

[0147] The inverse emulsion breaking compositions or multiply charged cationic or anionic compounds can be used to break inverse or multiple emulsions in production fluids in oil and gas applications.

[0148] The production fluid into which the inverse emulsion breaking composition or the multiply charged cationic or anionic compound can be introduced can be an aqueous medium. The aqueous medium can include water, gas, oil, and optionally liquid hydrocarbons.

[0149] The production fluid into which the inverse emulsion breaking composition or the multiply charged cationic or anionic compound can be introduced can be a liquid containing a hydrocarbon. The liquid hydrocarbon can be any type of liquid hydrocarbon, including, but not limited to, crude oil, heavy oil, processing residual oil, bituminous oil, coker oil, coker gas oil, fluid catalytic cracking feedstock, gas oil, naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, and kerosene. The production fluid can be a refined hydrocarbon product.

[0150] The production fluid or gas treated with the inverse emulsion breaking composition or the multiply charged cationic or anionic compound may be at any selected temperature, such as ambient temperature or elevated temperature. The fluid (e.g., liquid hydrocarbon) or gas may be at a temperature of about 40°C to about 250°C. The fluid or gas may be at a temperature of about -50°C to about 300°C, about 0°C to about 200°C, about 10°C to about 100°C, or about 20°C to about 90°C. The fluid or gas may be at a temperature of about 22°C, about 23°C, about 24°C, about 25°C, about 26°C, about 27°C, about 28°C, about 29°C, about 30°C, about 31°C, about 32°C, about 33°C, about 34°C, about 35°C, about 36°C, about 37°C, about 38°C, about 39°C, or about 40°C. The fluid or gas can be at a temperature of about 85°C, about 86°C, about 87°C, about 88°C, about 89°C, about 90°C, about 91°C, about 92°C, about 93°C, about 94°C, about 95°C, about 96°C, about 97°C, about 98°C, about 99°C, or about 100°C.

[0151] The inverse emulsion breaking composition or multiply charged cationic or anionic compounds can be added to the production fluid at various levels of water content. For example, the water content can be 0% to 100% volume / volume (v / v), 1% to 80% v / v, or 1% to 60% v / v. The production fluid can be an aqueous medium containing various levels of salinity. The fluid can have a salinity of 0% to 25%, about 1% to 24%, or about 10% to 25% weight / weight (w / w) total dissolved solids (TDS).

[0152] The production fluid or gas into which the inverse emulsion breaking composition or the multiply charged cationic or anionic compound is introduced can be contained and / or exposed to many different types of equipment. For example, the fluid or gas can be contained in equipment that transports the fluid or gas from one point to another, such as an oil and / or gas pipeline. The equipment can be part of an oil and / or gas refinery, such as a pipeline, a separation vessel, a dehydration unit, or a gas line. The fluid can be contained and / or exposed to equipment used in the extraction and / or production of oil, such as a wellhead. The equipment can be a cargo ship, a storage ship, a storage tank, or a pipeline connecting tanks, ships, or processing units.

[0153] The inverse emulsion breaking composition or multiply charged cationic or anionic compounds can be introduced into the production fluid or gas by any suitable method to ensure dispersion throughout the fluid.

[0154] The reverse emulsion breaking composition or multiply charged cationic or anionic compounds can be added at a point in the flow line upstream from the point where the production fluid is processed. For example, the reverse emulsion breaking composition or multiply charged cationic or anionic compounds can be injected using mechanical devices such as chemical injection pumps, pipe tees, injection fittings, atomizers, quills, etc.

[0155] The reverse emulsion breaking composition or the multiply charged cationic or anionic compound may be pumped into an oil and / or gas pipeline using an umbilical line. A capillary injection system may be used to deliver the reverse emulsion breaking composition or the multiply charged cationic or anionic compound to a selected fluid.

[0156] The reverse emulsion breaking composition or the multiply charged cationic or anionic compounds can be introduced into liquids and mixtures of several liquids, liquids and gases, liquids, solids, and gases. The reverse emulsion breaking composition or the multiply charged cationic or anionic compounds can be injected into a gas stream as an aqueous or non-aqueous solution, mixture, or slurry.

[0157] The production fluid or gas may be passed through an absorption tower containing an inverse emulsion breaking composition or a multiply charged cationic or anionic compound.

[0158] The reverse emulsion breaking composition or multiply charged cationic or anionic compound can be applied to the production fluid or gas to provide any selected concentration. In practice, the reverse emulsion breaking composition or multiply charged cationic or anionic compound is typically added to a flow line to provide an effective treatment dosage of from about 0.01 to about 5,000 ppm of the reverse emulsion breaking composition or multiply charged cationic or anionic compound. The reverse emulsion breaking composition or multiply charged cationic or anionic compound can be applied to the production fluid or gas to provide an active concentration of from about 1 parts per million (ppm) to about 1,000,000 ppm, from about 1 parts per million (ppm) to about 100,000 ppm, or from about 10 ppm to about 75,000 ppm. The multiply charged cationic or anionic compounds or salts / compositions thereof can be applied to the fluid to provide an active concentration of about 25 ppm to about 10,000 ppm, about 25 ppm to about 100 ppm, about 50 ppm to about 100 ppm, about 100 ppm to about 10,000 ppm, about 200 ppm to about 8,000 ppm, or about 500 ppm to about 6,000 ppm. By active concentration is meant the concentration of the reverse emulsion breaking composition or the multiply charged cationic or anionic compounds.

[0159] The reverse emulsion breaking composition or multiply charged cationic or anionic compounds can be applied to the production fluid or gas to provide an active concentration of about 0.1 ppm, about 0.5 ppm, about 1 ppm, about 2 ppm, about 5 ppm, about 10 ppm, about 20 ppm, about 100 ppm, about 200 ppm, about 500 ppm, or about 1,000 ppm in the treated production fluid. The reverse emulsion breaking composition or multiply charged cationic or anionic compounds can be applied to the production fluid to provide an active concentration of about 0.125 ppm, about 0.25 ppm, about 0.625 ppm, about 1 ppm, about 1.25 ppm, about 2.5 ppm, about 5 ppm, about 10 ppm, or about 20 ppm in the treated production fluid. Each production fluid may have its own dosage level requirements, and the effective dosage level of the reverse emulsion breaking composition or multiply charged cationic and anionic compounds to sufficiently break inverse emulsions or multiple emulsions may vary depending on the production fluid in which it is used.

[0160] The reverse emulsion breaking composition or the multiply charged cationic or anionic compound may be applied continuously, in batches, or a combination thereof. The administration of the reverse emulsion breaking composition or the multiply charged cationic or anionic compound may be continuous. The administration of the reverse emulsion breaking composition or the multiply charged cationic or anionic compound may be intermittent (e.g., batch treatment), or may be continuous / maintained and / or intermittent.

[0161] The dosage rate for continuous processing is typically in the range of about 10 to about 500 ppm, or about 10 ppm to about 200 ppm. The dosage rate for continuous processing is typically in the range of about 10 ppm to about 400,000 ppm, or about 10 ppm to about 20,000 ppm. The inverse emulsion breaking composition or multiply charged cationic or anionic compound can be applied as tablets to the pipeline to provide a high dosage (e.g., 20,000 ppm) of the composition.

[0162] The flow velocity of the flow lines in which the reverse emulsion breaking composition or multiply charged cationic or anionic compounds are used can be from 0.1 to 100 feet per second, or from 0.1 to 50 feet per second. The reverse emulsion breaking composition or multiply charged cationic or anionic compounds can also be formulated with water to facilitate addition to the flow lines.

[0163] Reverse emulsion breaking composition or multiply charged cationic or anionic compound can be dispensed by any suitable method generally known to those skilled in the art.For example, spray-type dispenser can be used.Spray-type dispenser works by impinging water spray on the exposed surface of the composition to dissolve a portion of the composition, and then immediately directs the concentrate solution containing the composition from the dispenser to a storage reservoir or directly to the point of use.

[0164] The reverse emulsion breaking composition or multiply charged cationic or anionic compound may be dispensed by intermittent or continuous immersion into water or production fluid. The reverse emulsion breaking composition or multiply charged cationic or anionic compound may then be dissolved, for example, at a controlled or predetermined rate. This rate may be effective to maintain a concentration of dissolved compound or composition that is effective for use according to the methods disclosed herein.

[0165] The inverse emulsion breaking compositions disclosed herein may comprise from about 10% to about 90% by weight of a carrier, a biocide, a corrosion inhibitor, an additional REB agent, a combination thereof, and from about 10% to about 90% by weight of one or more multiply charged cationic or anionic compounds, from about 20% to about 80% by weight of a carrier, a biocide, a corrosion inhibitor, an additional REB agent, or a combination thereof, and from about 20% to about 80% by weight of one or more multiply charged cationic or anionic compounds, from about 30% to about 70% by weight of a carrier, a biocide, a corrosion inhibitor, an additional REB agent, or a combination thereof, and from about 30% to about 70% by weight of one or more multiply charged cationic or anionic compounds, or from about 40% to about 60% by weight of a carrier, a biocide, a corrosion inhibitor, an additional REB agent, a combination thereof, and from about 40% to about 60% by weight of one or more multiply charged cationic or anionic compounds.

[0166] Additionally, when the inverse emulsion breaker is used to break emulsions on production fluids in oil and gas operations, the optional emulsion breaker and inverse emulsion breaking composition can be added to the production fluids.

[0167] The emulsion breaker can include oxyalkylated phenol-formaldehyde resins, resin esters, oxyalkylated polyalkylamines, polyols, crosslinked polyols with di- or polyfunctional crosslinkers, isocyanates, acids, or combinations thereof.

[0168] The reverse emulsion breaking composition can include a mixture of the reverse emulsion breaker and one or more emulsion breakers, depending on the properties of the production fluid.

[0169] In some cases, the emulsion breaker and the inverse emulsion breaker have a synergistic effect for breaking up water-in-oil-in-water emulsions in the production fluids of the oil production system. The emulsion breaker can have a concentration of about 100 ppm to about 400 ppm in the production fluids.

[0170] A diluent can be added to the production fluid, and the diluent can be condensate, naphtha, kerosene, light crude oil, or a combination thereof. In some embodiments, the REB compositions disclosed herein further comprise a diluent. In some other embodiments, the REB compositions disclosed herein further comprise a diluent and one or more emulsion breakers.

[0171] Suitable diluents suitable for or for use with the REB compositions disclosed herein include, but are not limited to, naphtha-based diluents and synthetic crude oil (SCO). Naphtha-based diluents have a typical density of 650-750 kg / m3 and are typically used in production fluids with high bitumen content (e.g., 70 wt%). SCO has a typical density of 650-750 kg / m3 and is typically used in production fluids with low bitumen content (e.g., 50 wt%).

[0172] In some embodiments, a suitable diluent for the REB compositions disclosed herein is a combination of C4-C5 hydrocarbons and some aromatic hydrocarbons, which vary depending on the cost and nature of the production fluid being treated.

[0173] In some embodiments, the diluent is about 5% to about 35% by weight of the REB composition. In some other embodiments, the diluent is about 5% to about 15% by weight, about 10% to about 20% by weight, about 10% to about 30% by weight, about 15% to about 20% by weight, about 15% to about 25% by weight, about 15% to about 30% by weight, about 15% to about 35% by weight, about 20% to about 25% by weight, about 25% to about 35% by weight, about 30% to about 35% by weight, or about 10% to about 30% by weight of the REB composition.

[0174] The inverse emulsion breaking compositions disclosed herein are preferably added to the influent emulsion to a water and oil separation system. The emulsion breaker, inverse emulsion breaker, or a combination thereof can be added to an injection point in the influent pipeline of the production fluid before the production fluid enters one or more separation vessels. When the inverse emulsion breaker is combined with an optional emulsion breaker, they can be injected independently, simultaneously, or sequentially. Additionally, the diluent can be injected at a different injection point. The separation vessel can be a free water knockout (FWKO) vessel, a thermal treater, or a phase separator.

[0175] The effectiveness of an inverse emulsion breaking composition depends on a number of factors such as water droplets (WD), water quality, interface quality, oil drying, and the like.

[0176] In one aspect, provided herein are compounds derived from an aza-Michael addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) bearing an ionizable group according to one of the following formulas: [ka] In the formula, X is NH or O, and R 2 But, H, CH 3 or unsubstituted linear or branched C 2 ~C 10 is an alkyl, alkenyl, or alkynyl group; R 2’ But, H, CH 3 or unsubstituted or substituted linear or branched chain C 1 ~C 10 Alkyl, alkenyl, alkynyl groups, -COOH, -CH 2 COOH, Y', or -(CH 2 ) m -Y', m is an integer from 2 to 4, and R 3 is absent or unsubstituted linear or branched chain C 1 ~C 30 is an alkylene group, and Y is -NR 4 R 5R 6 (+) and Y' is -COOH, -SO 3 H, -PO 3 H, -OSO 3 H, -OPO 3 H, or a salt thereof; R 4 , R 5 , and R 6 became independent, C 1 ~C 10 Disclosed are compounds wherein the alkyl group is an alkyl group, and the compound is a multiply charged cationic compound, having two or more positive charges, or a multiply charged anionic compound, having two or more negative charges.

[0177] In some embodiments, the polyamine is NH 2 -[R 10’ ] n -NH 2 , (RNH) n -RNH 2 , H 2 N-(RNH) n -RNH 2 , or H 2 N-(RN(R')) n -RNH 2 where R 10’ is linear or branched, unsubstituted or substituted C 2 ~C 10 alkylene groups, or combinations thereof, and R is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 alkylene groups, or combinations thereof, where R' is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2-, linear or branched unsubstituted or substituted C 4 ~C 10 Alkyl group, RNH 2 , R.N.H.R.N.H. 2 , or RN(RNH 2 ) 2 and n can be from 2 to 1,000,000.

[0178] The structure of and the reactions leading to an exemplary multiply charged cationic compound (I) using linear polyethyleneimine is shown in Figure 1. A scheme for preparing an exemplary cationic polymer composition (II) using branched polyethyleneimine is shown in Figure 2.

[0179] In FIG. 1 and FIG. 2, k, l, m, n, o, or p is an integer from 1 to 100, X is NH or O, and R 2 But, H, CH 3 or unsubstituted linear or branched C 2 ~C 10 is an alkyl group, R 3 is absent or unsubstituted linear or branched chain C 1 ~C 30 is an alkylene group, and Y is -NR 4 R 5 R 6(+) or a salt thereof, R 4 , R 5 , and R 6 became independent, C 1 ~C 10 It is an alkyl group or a benzyl group.

[0180] Structures I and II in Figures 1 and 2 are generalized depictions of exemplary reaction products. In structures I and II, all secondary and primary amines of the polyethyleneimine react with the activated olefin, so no secondary amines remain. In the disclosed multiply charged cationic or anionic compounds, some secondary or primary amine groups may not fully react with the activated olefin and remain as primary or secondary amine groups in the multiply charged cationic or anionic compounds or salts thereof.

[0181] In other words, in some embodiments, the multiply charged cationic or anionic compound is NA 2 -[R 10’ ] n -NA 2 , (RNA) n -RNA 2 , A 2 N-(RNA) n -RNA 2 , or A 2 N-(RN(R')) n -RNA 2 wherein R 10’ is linear or branched, unsubstituted or substituted C 2 ~C 10 alkylene groups, or combinations thereof, and R is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 alkylene groups, or combinations thereof, where R' is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 Alkyl groups, RNA 2 , RNA 2 , or RN(RNA 2 ) 2 where n can be from 2 to 1,000,000, and A is H or [ka] or one of a combination thereof, wherein each compound contains at least two aprotic and cationic or anionic A groups, at least three aprotic and cationic or anionic A groups, at least four aprotic and cationic or anionic A groups, at least five aprotic and cationic or anionic A groups, or six or more cationic or anionic A groups. In some embodiments, A is H or a positively charged [ka] In some other embodiments, A is H or a negatively charged [ka] It is.

[0182] In some embodiments, the primary NH 2 At least two of the protons are [ka] and first-class NH 2 The remainder of the protons remain. In some embodiments, the primary NH 2 At least two of the protons are [ka] and first-class NH 2 The remainder of the protons remain. In some other embodiments, all primary NH 2 Protons are [ka] In some embodiments, the primary NH 2 and some of the secondary NH protons are [ka] In some embodiments, all primary NH 2and some of the secondary NH protons are [ka] is replaced by.

[0183] In some embodiments of the compounds disclosed herein, X is NH. In some other embodiments, X is O.

[0184] In some embodiments, R 2 is H. In some embodiments, R 2 is CH 3 In yet some other embodiments, R 2 is CH 3 CH 3 , C.H. 2 CH 2 CH 3 , or CH(CH 3 ) 2 It is.

[0185] In some embodiments, Y is -NR 4 R 5 R 6 (+) In some other embodiments, Y is -NR 4 R 5 R 6 (+) and R 4 , R 5 , and R 6 is independent, CH 3 In yet some other embodiments, Y is -NR 4 R 5 R 6 (+) and R 4 and R 5 is independent, CH 3 and R 6 is C 2 ~C 12 In some other embodiments, Y is -NR 4 R 5 R 6 (+) and R4 and R 5 is independent, CH 3 and R 6 -CH 2 -C 6 H 6 It is.

[0186] In some embodiments, Y is -NR 4 R 5 R 6 (+) and the counterion of Y is a negatively charged ion or species. In some other embodiments, the counterion of Y is chloride, bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate, carbonate, bicarbonate, hydrogen oxalate, hydrogen sulfate, hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

[0187] In some embodiments, Y' is -COOH or a salt thereof. In some other embodiments, Y' is -SO 3 H, -OSO 3 H, or a salt thereof. In yet some other embodiments, Y' is -OPO 3 H, -PO 3 H, or a salt thereof. In some other embodiments, Y' is an acid species or a salt thereof.

[0188] In some embodiments, R 3 is CH 2 In some other embodiments, R 3 is CH 2 CH 2 In another embodiment, R 3 is C(CH 3 ) 2 In yet some other embodiments, R 3 is unsubstituted, linear, and saturated C 1 ~C 10 In some embodiments, R is an alkylene group. 3 is unsubstituted, linear, and unsaturated C 1 ~C 10It is an alkylene group.

[0189] In some embodiments, R 3 is a linear C 8 ~C 18 In some other embodiments, R is an alkyl, alkenyl, or alkynyl group. 3 is a branched chain C 8 ~C 20 It is an alkyl, alkenyl, or alkynyl group.

[0190] In some embodiments, the polyamine is -[RNH] n -, where R is -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 an alkylene group, an alkylene group, or a combination thereof, and n is an integer of 3, 4, 5, 6, 7 to 9, or 10 to 1,000,000.

[0191] In some embodiments, the polyamine is (RNH) n -RNH 2 where R is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 an alkylene group, an alkylene group, or a combination thereof, where n can be from 2 to 1,000,000. In some embodiments, R is the same in each monomer. In some other embodiments, R can vary from one monomer to another.

[0192] In some other embodiments, the polyamine is H 2 N-(RNH) n -RNH 2 where R is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched, unsubstituted or substituted C 4 ~C 10 an alkylene group, an alkylene group, or a combination thereof, where n can be from 2 to 1,000,000. In some embodiments, R is the same in each monomer. In some other embodiments, R can vary from one monomer to another.

[0193] In yet some other embodiments, the polyamine is H 2 N-(RN(R')) n -RNH 2 where R is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 alkylene groups, or combinations thereof, where R' is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 Alkyl group, RNH 2, R.N.H.R.N.H. 2 , or RN(RNH 2 ) 2 and n can be from 2 to 1,000,000. In some embodiments, R or R' is the same in each monomer. In some other embodiments, R or R' can vary from one monomer to another.

[0194] In some embodiments, the polyamine is NH 2 -[R 10’ ] n -NH 2 wherein R 10’ is linear or branched, unsubstituted or substituted C 4 ~C 10 In some other embodiments, R is an alkylene group, an alkylene group, or a combination thereof, and n is an integer of 3, 4, 5, 6, 7 to 9, or 10 to 1,000,000. 10’ can vary from one monomer to another.

[0195] In some embodiments, the polyamine is one or more polyamines based on JEFFAMINE® by Huntsman.

[0196] In some embodiments, the polyamine comprises an alkyleneamine, the alkyleneamine comprising ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, tris(2-aminoethyl)amine, or a mixture thereof.

[0197] In some other embodiments, the polyamine is a mixture of monoamines, diamines, and triamines having a polyether backbone or a polyether backbone based on propylene oxide (PO), ethylene oxide (EO), or a mixture of both oxides.

[0198] In some embodiments, the polyamine is an unmodified polyamine. In some other embodiments, the polyamine is a modified polyamine. As used herein, "modified polyamine" refers to a polyamine in which one or more NH protons are replaced by an aprotic group, such as an alkyl.

[0199] Further, in some embodiments, the polyamine is an ethoxylated polyamine, a propylated polyamine, a polyquat-bearing polyamine, a polyglycerol-bearing polyamine, or a combination thereof.

[0200] In some embodiments, the polyamine has an average molecular weight (M) of about 130 to about 4,000. w ) is a diamine or triamine having the formula:

[0201] In yet some other embodiments, the polyamine is a linear, branched, or dendritic polyethyleneimine. In some other embodiments, the polyamine contains only primary and secondary amine groups. In some embodiments, the polyamine contains only primary, secondary, and tertiary amine groups. In some other embodiments, the polyamine contains only primary and tertiary amine groups.

[0202] In some embodiments, the polyamine is a single compound, hi some other embodiments, the polyamine is a mixture of two or more different polyamines, the different polyamines having different molecular weights, different structures, or both.

[0203] In some embodiments, the polyamine has an average molecular weight (M) of about 130 to about 2,000,000 Da. w In some other embodiments, the polyamine has an average molecular weight (M) of about 130 to about 5,000 Da. w In yet some other embodiments, the polyamine has an average molecular weight (M) of about 130 to about 25,000 Da. w ).

[0204] In some embodiments, the polyamine is from about 60 to 200, from about 100 to 400, from about 100 to 600, from about 600 to 5,000, from about 600 to 800, from about 800 to 2,000, from about 800 to 5,000, from about 100 to 2,000,000, from about 100 to 25,000, from about 600 to 25,000, from about 800 to 25,000, from about 600 to 750,000, from about 800 to 750,000, from about 25,000 to 750,000, from about 750,000 to 2, 000,000, about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 1,000, about 1,500, about 2,000, about 3,000, about 5,000, about 8,000, about 10,000, about 15,000, about 20,000, about 50,000, about 100,000, about 250,000, about 500,000, about 1,000,000, about 2,000,000, or any value therebetween. w ).

[0205] In some embodiments, the compound is a mixture derived from linear polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC). In some other embodiments, the compound is a mixture derived from linear polyethyleneimine and [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC).

[0206] In some other embodiments, the multiply charged cationic or anionic compound is a mixture derived from branched polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC). In some other embodiments, the compound is a mixture derived from linear polyethyleneimine and [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC).

[0207] In some embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethanaminium methylsulfate (DMAEA-MSQ), or 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MSQ).

[0208] In some other embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), or a mixture thereof.

[0209] In some embodiments, the activated olefin is 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethanaminium methylsulfate (DMAEA-MSQ), 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MSQ), or a mixture thereof.

[0210] In some embodiments, the activated olefin is acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinyl sulfonic acid, vinyl phosphonic acid, or mixtures thereof.

[0211] In some other embodiments, the activated olefin is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 3-(allyloxy)-2-hydroxypropane-1-sulfonate, or a mixture thereof.

[0212] In some other embodiments, the activated olefin is vinyl sulfonic acid, vinyl phosphonic acid, or a mixture thereof.

[0213] In yet some other embodiments, when the activated olefin contains an anionic group capable of carrying a negative charge at alkaline pH, the counter cation for the negative charge can be an alkali metal ion, Li + , Na + , K + , N.H. 4 + , quaternary ammonium ions, and the like, but are not limited to these.

[0214] In some embodiments, the compound is an aza-Michael addition reaction product of (3-acrylamidopropyl)trimethylammonium chloride (APTAC) with tetraethylenepentamine, E-100 (a mixture of tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and hexaethyleneheptamine (HEHA)), pentaethylenehexamine (PEHA), or diethylenetriamine (DETA), respectively.

[0215] In some embodiments, the compounds are (3-acrylamidopropyl)trimethylammonium chloride (APTAC) and 3-(3-(4-methylphenyl)-2-propanediol), each of which has an average molecular weight (M w ), polyethyleneimine having an average molecular weight (M w ), polyethyleneimine having an average molecular weight (M w ), or polyethyleneimine having an average molecular weight (M w ) is an aza-Michael addition reaction product with polyethyleneimine.

[0216] In some embodiments, the compound is [ka] where n=0 to 1000. It should be understood that when n is greater than 2, the compound may be a mixture of three or more cationic compounds, which differ from each other in the exact location of the NH replacement.

[0217] In some other embodiments, the compound is [ka] It is.

[0218] In some other embodiments, the compound is [ka] It is.

[0219] In some other embodiments, the compound is [ka] It is.

[0220] In some embodiments, the multiply charged cationic or anionic compounds have an average molecular weight (M) of about 100 to about 2,000,000 Da. w In some other embodiments, the multiply charged cationic or anionic compound has an average molecular weight (M) of about 100 to about 50,000 Da. w In yet some other embodiments, the multiply charged cationic or anionic compounds have an average molecular weight (M) of about 100 Da to about 600 Da, about 100 Da to about 1,000 Da, about 100 Da to about 1,400 Da, about 100 Da to about 3,000 Da, about 100 Da to about 5,500 Da, or about 100 Da to about 10,000 Da, about 100 Da to about 20,000 Da, about 100 Da to about 30,000 Da, or about 100 Da to about 40,000 Da. w ).

[0221] In some embodiments, the multiply charged cationic compound has at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or at least 10 positive charges. In some other embodiments, the compound has between 10 and 1000 positive charges, or any value in between.

[0222] In some embodiments, the multiply charged cationic compounds have at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or at least 10 negative charges. In some other embodiments, the compounds have between 10 and 1000 positive charges, or any value between negative charges.

[0223] In some embodiments, the compounds are water-soluble or water-dispersible.

[0224] Method of preparation In another aspect, provided herein is a method of making a compound or a salt thereof, the method comprising contacting a polyamine with an activated olefin (Michael acceptor) having an ionizable group according to one of the following formulas: [ka] In the formula, X is NH or O, and R 2 But, H, CH 3 or unsubstituted linear or branched C 2 ~C 10 is an alkyl, alkenyl, or alkynyl group; R 2’ But, H, CH 3 or unsubstituted or substituted linear or branched chain C 1 ~C 10 Alkyl, alkenyl, alkynyl groups, -COOH, -CH 2 COOH, Y', or -(CH 2 ) m -Y', m is an integer from 2 to 4, and R 3 is absent or unsubstituted linear or branched chain C1 ~C 30 is an alkylene group, and Y is -NR 4 R 5 R 6 (+) and Y' is -COOH, -SO 3 H, -PO 3 H, -OSO 3 H, -OPO 3 H, or a salt thereof; R 4 , R 5 , and R 6 became independent, C 1 ~C 10 A method is disclosed in which an alkyl group, a polyamine and an activated olefin undergo an aza-Michael addition reaction, and the compound is a multiply charged cationic compound having two or more positive charges, or a multiply charged anionic compound having two or more negative charges.

[0225] In some embodiments of the disclosed methods, the polyamine is NH 2 -[R 10’ ] n -NH 2 , (RNH) n -RNH 2 , H 2 N-(RNH) n -RNH 2 , H 2 N-(RN(R')) n -RNH 2 or a mixture thereof, wherein R 10’ is linear or branched, unsubstituted or substituted C 2 ~C 10 alkylene groups, or combinations thereof, and R is -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 alkylene groups, or combinations thereof, where R' is -CH 2 -, -CH2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, linear or branched unsubstituted or substituted C 4 ~C 10 Alkyl group, RNH 2 , R.N.H.R.N.H. 2 , or RN(RNH 2 ) 2 and n can be from 2 to 1,000,000.

[0226] In another embodiment, the activated olefin is [ka] where X is NH or O, and R 2 But, H, CH 3 or unsubstituted linear or branched C 2 ~C 10 is an alkyl, alkenyl, or alkynyl group; R 3 is absent or unsubstituted linear or branched chain C 1 ~C 30 is an alkylene group, and Y is -NR 4 R 5 R 6 (+) and R 4 , R 5 , and R 6 became independent, C 1 ~C 10 It is an alkyl group.

[0227] In some embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethanaminium methylsulfate (DMAEA-MSQ), 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MSQ), or a mixture thereof.

[0228] In some embodiments, Y is -NR 4 R 5 R 6 (+) and the counterion of Y is a negatively charged ion or species. In some other embodiments, the counterion of Y is chloride, bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate, carbonate, bicarbonate, hydrogen oxalate, hydrogen sulfate, hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

[0229] In some embodiments of the disclosed methods, the activated olefin is [ka] where X is NH or O, and R 2 But, H, CH 3 or unsubstituted linear or branched C 2 ~C 10 is an alkyl, alkenyl, or alkynyl group; R 2’ But, H, CH 3 or unsubstituted or substituted linear or branched chain C 1 ~C 10 Alkyl, alkenyl, alkynyl groups, -COOH, -CH 2 COOH, Y', or -(CH2 ) m -Y', m is an integer from 2 to 4, and R 3 is absent or unsubstituted linear or branched chain C 1 ~C 30 An alkylene group, and Y' is -COOH, -SO 3 H, -PO 3 H, -OSO 3 H, -OPO 3 H, or a salt thereof; R 4 , R 5 , R 6 became independent, C 1 ~C 10 It is an alkyl group.

[0230] In some embodiments, the activated olefin is acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinyl sulfonic acid, vinyl phosphonic acid, or mixtures thereof.

[0231] In some other embodiments, the activated olefin is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 3-(allyloxy)-2-hydroxypropane-1-sulfonate, or a mixture thereof.

[0232] In yet some other embodiments, when the activated olefin contains an anionic group capable of carrying a negative charge at alkaline pH, the counter cation for the negative charge can be an alkali metal ion, Li + , Na + , K + , N.H. 4 + , quaternary ammonium ions, and the like, but are not limited to these.

[0233] In some embodiments of the disclosed method, the contacting step is carried out in the presence of a reaction solvent. The reaction solvent can be any inorganic or organic solvent commonly used in chemical synthesis. The reaction solvent used in the disclosed method can be introduced into the reaction between the polyamine and the activated olefin containing a cationic or anionic group by any method known to those skilled in the art. For example, the solvent can be added to the reaction vessel or tank simultaneously with one or both reactants, or after the polyamine, the activated olefin, or both are added.

[0234] In some embodiments, the reaction solvent is water, methanol, ethanol, propanol, glycol, PEG, or a mixture thereof, in some other embodiments, the reaction solvent is water.

[0235] In some other embodiments of the disclosed method, the contacting step is carried out in the presence of a catalyst, base, or acid. The catalyst, base, or acid can be introduced into the reaction between the polyamine and the activated olefin by any method known to one of skill in the art.

[0236] In some embodiments, the contacting step is carried out without the presence of an additional base or alkaline source. In some other embodiments, the contacting step is carried out in the presence of an alkaline source. In some other embodiments, the contacting step is carried out in the presence of an organic base, such as an alkanolamine. In yet some other embodiments, the contacting step is carried out in the presence of an alkali metal hydroxide, carbonate, imidazole / pyridine base, or combinations thereof, e.g., NaOH, Na 2 CO 3, aminoethylpyridine, aminopropylimidazole, or a combination thereof. In some other embodiments, the contacting step is carried out in the presence of benzyltrimethylammonium hydroxide. In some embodiments, the catalytic base is an amidine or guanidine base, or a mixture thereof. In some other embodiments, the catalyst is an ionic liquid, such as 1,8-diazabicyclo[5.4.0]-undec-7-en-8-ium acetate, for reaction under solvent-free conditions at room temperature.

[0237] In yet some other embodiments of the disclosed method, the contacting step is carried out in the presence of an acid. In some other embodiments, the contacting step is carried out in the presence of a catalyst. The catalyst can be any one or more of the catalysts known to those skilled in the art for the Michael addition reaction.

[0238] In yet some other embodiments of the disclosed method, the contacting step is performed without a catalyst, a base, or an acid. In some other embodiments, the contacting step is performed without an alkali metal hydroxide, a carbonate, a silicate, a metasilicate, an imidazole / pyridine base, or all of the above. In some embodiments, the contacting step is performed without a base.

[0239] In yet another aspect, disclosed herein are articles, products, or compositions that include one or more compounds disclosed herein or produced by the methods disclosed herein.

[0240] In some embodiments, the article, product, or composition further comprises a carrier solvent or carrier. As used herein, a "carrier solvent" or carrier is a solvent or solvent system in which the disclosed compounds can be uniformly distributed and stable.

[0241] As used herein, "stable" means that a compound disclosed herein does not precipitate or separate from the carrier solvent or other components in the composition for about 1 hour, about 1 hour to about 12 hours, about 12 hours, about 1 day, about 5 days, about 10 days, about 20 days, about 1 month, about 1 month to about 1 year, or about 1 year to about 2 years after the compound disclosed herein and the carrier solvent or any other components are homogeneously mixed.

[0242] In some other embodiments, the carrier is water, an organic solvent, or a mixture thereof. In some embodiments, the article, product, or composition further comprises an organic solvent. In some embodiments, the article, product, or composition further comprises an organic solvent and water.

[0243] In some embodiments, the carrier solvent can be any inorganic or organic solvent commonly used in industry or in laboratories. In some other embodiments of the article, product, or composition, the carrier solvent is water, alcohol, alkylene glycol, alkylene glycol alkyl ether, or a combination thereof. In some other embodiments, the carrier solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

[0244] In some embodiments, the article, product, or composition is a solid. In some other embodiments, the article, product, or composition is a liquid.

[0245] In one aspect, disclosed herein are compositions for breaking up inverse emulsions in production fluids from oil and gas production systems, the inverse emulsion breaking compositions comprising one or more compounds or salts thereof disclosed herein and one or more inverse emulsion breaking agents. In some embodiments, the inverse emulsion compositions break oil-in-water emulsions in the production fluids.

[0246] In another aspect, disclosed herein is a method of breaking up inverse emulsions in a production fluid from an oil and gas production system, the method comprising contacting a production fluid of the oil and gas production system with an inverse emulsion breaker (REB) composition to generate a treated production fluid, the inverse emulsion breaking composition comprising one or more compounds disclosed herein and one or more inverse emulsion breaking agents. In some embodiments, the inverse emulsion composition breaks an oil-in-water emulsion in the production fluid.

[0247] In some embodiments, the production fluid comprises an oil-in-water emulsion, a water-in-oil-in-water emulsion, or both, hi some other embodiments, the production fluid comprises crude oil, refined oil, bitumen, condensate, slop oil, distillate, fuel, or mixtures thereof.

[0248] In some embodiments, the produced fluid comprises fresh water, recycled water, salt water, surface water, produced water, or mixtures thereof. In some embodiments, the produced fluid comes from an oil well, a downhole formation, or a geothermal well.

[0249] In some embodiments, the production fluid is from a steam-assisted gravity drainage (SAGD) process, and the production fluid includes bitumen and water, hi some other embodiments, the production fluid is produced water, which is the water portion of the production fluid after oil and dirt have been removed.

[0250] In some embodiments, the compound or modified compound is soluble or dispersible in water or the inverse emulsion breaking composition.

[0251] In some embodiments, the reverse emulsion breaking composition further comprises one or more additional reverse emulsion breaking composition agents.

[0252] In some embodiments, the inverse emulsion breaking composition comprises a carrier, wherein the carrier is water, an organic solvent, or a mixture thereof.

[0253] In some embodiments, the reverse emulsion breaking composition further comprises an organic solvent. In some other embodiments, the reverse emulsion breaking composition further comprises an organic solvent and water.

[0254] In some embodiments, the organic solvent is an alcohol, a hydrocarbon, a ketone, an ether, an alkylene glycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, or any combination thereof. In some other embodiments, the organic solvent is an alcohol, an alkylene glycol, an alkylene glycol alkyl ether, or a combination thereof. In still some embodiments, the organic solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

[0255] In some embodiments, the organic solvent is methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, methylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutyl ketone, diethyl ether, propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, mixtures thereof with water, or any combination thereof.

[0256] In some embodiments, the reverse emulsion breaking composition further comprises one or more of a corrosion inhibitor. In some embodiments, the reverse emulsion breaking composition further comprises one or more of a corrosion inhibitor and a carrier. In some embodiments, the corrosion inhibitor is an imidazoline compound, a pyridinium compound, or a combination thereof.

[0257] In some embodiments, the reverse emulsion breaking composition does not include a corrosion inhibitor.

[0258] In some embodiments, the reverse emulsion breaking composition further comprises a biocide. In some embodiments, the reverse emulsion breaking composition further comprises a biocide and a carrier. In some other embodiments, the reverse emulsion breaking composition further comprises a biocide, a corrosion inhibitor, and a carrier.

[0259] In some other embodiments, the biocide is chlorine, hypochlorite, ClO 2 , bromine, ozone, hydrogen peroxide, peracetic acid, peroxysulfates, glutaraldehyde, dibromonitrilopropionamide, isothiazolones, terbuthylazine, polymeric biguanides, methylene bisthiocyanate, tetrakishydroxymethylphosphonium sulfate, and any combination thereof.

[0260] In some embodiments, the inverse emulsion breaking composition does not include a biocide.

[0261] In some embodiments, the inverse emulsion breaking composition further comprises an organosulfur compound. In some other embodiments, the organosulfur compound is a mercaptoalkyl alcohol, mercaptoacetic acid, thioglycolic acid, 3,3'-dithiodipropionic acid, sodium thiosulfate, thiourea, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, sodium metabisulfite, or a combination thereof.

[0262] In some embodiments, the reverse emulsion breaking composition further comprises an acid. In some embodiments, the reverse emulsion breaking composition further comprises an inorganic acid, a mineral acid, an organic acid, or a mixture thereof. In some embodiments, the reverse emulsion breaking composition comprises from about 1% to about 20%, from about 1% to about 15%, from about 1% to about 10%, or from about 1% to about 5% by weight of an acid.

[0263] In some embodiments, the acid is hydrochloric acid, hydrofluoric acid, citric acid, formic acid, acetic acid, or a mixture thereof.

[0264] In some embodiments, the inverse emulsion breaking composition further comprises a hydrogen sulfide scavenger. In some other embodiments, the hydrogen sulfide scavenger is an oxidizer, an inorganic peroxide, sodium peroxide, chlorine dioxide; 1 ~C 10 The triazine may be an aldehyde, formaldehyde, glyoxal, glutaraldehyde, acrolein or methacrolein, triazine, monoethanolamine triazine, monomethylamine triazine, or a mixture thereof.

[0265] In some embodiments, the reverse emulsion breaking composition further comprises a surfactant.In some embodiments, the reverse emulsion breaking composition further comprises a surfactant, a biocide, and a carrier.

[0266] In some embodiments, the surfactant is a nonionic, cationic, anionic, amphoteric, zwitterionic, gemini, dicationic, dianionic surfactant, or mixtures thereof.

[0267] In some embodiments, the surfactant is an alkylphenol, a fatty acid, or a mixture thereof.

[0268] In some embodiments, the inverse emulsion breaking composition further comprises an asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, a gas hydrate inhibitor, a pH adjuster, or any combination thereof.

[0269] In some embodiments, the reverse emulsion breaking composition further comprises a coagulant / flocculant, a water clarifier, or a mixture thereof. In some embodiments, the reverse emulsion breaking composition further comprises an additional reverse emulsion breaker, a carrier, a corrosion inhibitor, a coagulant / flocculant, a water clarifier, or a mixture thereof.

[0270] In some embodiments, the reverse emulsion breaking composition further comprises an additional reverse emulsion breaker.In some embodiments, the reverse emulsion breaking composition further comprises an additional reverse emulsion breaker, a carrier, and a corrosion inhibitor.

[0271] In some embodiments, the reverse emulsion breaking composition further comprises an additional reverse emulsion breaker, emulsion breaker, or mixtures thereof.

[0272] In some embodiments, the emulsion breaker or additional REBs contact the production fluid independently, simultaneously, or sequentially. In some other embodiments, the emulsion breaker or additional REBs contact the production fluid via a multiply charged compound in the REB composition or via a separate composition.

[0273] In some embodiments, additional inverse emulsion breakers are organic polymers such as acrylic acid-based polymers, acrylamide-based polymers, polymerized amines, alkanolamines, thiocarbamates, and cationic polymers such as acrylamide diallyldimethylammonium chloride (DADMAC) polymers and / or methylacrylamide [3-(methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) polymers, copolymers of epichlorohydrin and dimethylamine or trimethylamine, copolymers of acrylamide and dimethylaminoethyl acrylate (quaternized methyl chloride, aluminum chlorohydrate (ACH) and polyaluminum chloride (PAC), acrylamide), DMAEA.MCQ copolymers.

[0274] In some embodiments, the reverse emulsion breaking composition further comprises a dispersant.

[0275] In some embodiments, the reverse emulsion breaking composition comprises an antioxidant, a polymer decomposition inhibitor, a permeability control agent, a foaming agent, a defoaming agent, an emulsifier, a CO 2 and / or O 2 The composition may further comprise a scavenger, gelling agent, lubricant, friction reducer, salt, alkalinity source, or mixtures thereof for use in the preparation of the composition.

[0276] In some embodiments, the inverse emulsion breaking composition (REB) is a liquid, a gel, or a mixture containing a liquid / gel and a solid. In some embodiments, the REB composition is a solid or a liquid.

[0277] In some embodiments, the reverse emulsion breaking composition or use solution thereof has a pH of about 2 to about 11.

[0278] In some embodiments, the reverse emulsion breaking composition comprises from about 10% to about 80% by weight of a multiply charged cationic or anionic compound disclosed herein, or a salt thereof. In some other embodiments, the REB composition comprises about 30% to about 70% by weight, about 20% to about 40% by weight, about 25% to about 30% by weight, about 10% to about 70% by weight, about 30% to about 60% by weight, about 40% to about 50% by weight, about 10% to about 30% by weight, about 20% to about 40% by weight, 30% to about 50% by weight, about 40% to about 60% by weight, about 50% to 70% by weight, about 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% by weight, or any value therebetween, of a multiply charged cationic or anionic compound disclosed herein or a salt thereof.

[0279] In some embodiments, the multiply charged cationic or anionic compounds or salts thereof disclosed herein have a concentration of about 1 ppm to about 200 ppm in the treated production fluid. In other embodiments, the multiply charged cationic or anionic compounds have a concentration of about 10 ppm to about 150 ppm in the treated production fluid after the REB composition is applied to the production fluid. In yet some other embodiments, the compounds have a concentration of about 10 ppm to about 75 ppm in the treated production fluid after the REB composition is applied to the production fluid.

[0280] Uses of the Disclosed Methods or Compositions In some embodiments, for the methods disclosed herein, providing a REB composition in a production fluid means that the REB composition or a multiply charged cationic or anionic compound, or a use solution thereof, is added to the production fluid. In some other embodiments, providing a REB composition in a production fluid means that the REB composition or a multiply charged cationic or anionic compound is added to a fluid that contacts or creates the production fluid. The REB composition or a multiply charged cationic or anionic compound, or a use solution thereof, may be added continuously or intermittently when more compound or composition may be needed.

[0281] As used herein, a use solution of a REB composition or a multiply charged cationic or anionic compound refers to a dilution solution for the composition or compound with a diluent. As used herein, a diluent refers to one of water, production fluid, or a carrier or solvent as defined herein. The REB composition or compound can be diluted 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 to 1,000,000 times, or any value therebetween, to generate a use solution, and then provide the use solution to the production fluid. In the present disclosure, when a REB composition or a multiply charged cationic or anionic compound is applied, either the composition / compound or its use solution is applied.

[0282] In some embodiments, the reverse emulsion breaking composition is provided to the aqueous system independently, simultaneously, or sequentially with one or more additional reverse emulsion breaking composition agents in the REB composition.

[0283] In some embodiments, the REB composition is diluted with water to create a use solution of the REB composition, and the use solution is then provided in the production fluid. In some embodiments, the water for diluting the REB composition includes fresh water, recycled water, salt water, surface water, produced water, or mixtures thereof. In some embodiments, the water for diluting the REB composition is the production fluid.

[0284] Typically, the REB composition or a use solution thereof is injected into the production fluid. In this context, the production fluid is the use solution of the REB composition. In some embodiments, the concentration of the REB composition is from about 1 ppm to about 1,000 ppm.

[0285] In some embodiments, the additional REB, flocculant, coagulant, or water purifying agent is [ka] The average molecular weight (M) of the monomer is about 20,000 to about 20,000,000 Da. w ), wherein R 31 , R 32 , and R 33 are independently hydrogen or alkyl; R 34 , R 35 , R 36 , R 37 , and R 38 is independently alkyl; p is an integer from 1 to 6; and m, n, and are integers.

[0286] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is another polymeric cationic, anionic, nonionic, inorganic coagulant / flocculant.

[0287] In some embodiments, the emulsion breaker, REB, flocculating agent, coagulant, or water purifying agent is an oxyalkylated phenol-formaldehyde resin, a resin ester, an oxyalkylated polyalkylamine, a polyol, a crosslinked polyol with a di- or polyfunctional crosslinker, an isocyanate, an acid, or a combination thereof.

[0288] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is aluminum sulfate, aluminum chloride, ferric sulfate, ferric chloride, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, magnesium oxide, magnesium hydroxide, or mixtures thereof.

[0289] In some embodiments, the emulsion breaker, REB, flocculating agent, coagulant, or water clarifier is a dendritic polyamine, a dendritic polyamidoamine, a hyperbranched polyethyleneimine, its reaction products with gluconolactone, an alkylene oxide, 3-chloro-2-hydroxypropanesulfonic acid, an alkyl halide, a benzyl halide, and a dialkyl sulfate, or mixtures thereof.

[0290] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is a polyepihalohydrin, a polyelectrolyte thereof, or a mixture thereof.

[0291] In some embodiments, the emulsion breaker, REB, flocculating agent, coagulant, or water clarifier is tridithiocarbamic acid, dithiocarbamic acid salts, dimethylaminoethyl acrylate methyl chloride, benzyl chloride quaternary salts, polymeric quaternary ammonium betaine, metal salts, zinc chloride, aluminum chloride, polymeric quaternary ammonium salts, copolymers of acrylic acid and acrylamide, or mixtures thereof.

[0292] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is a high molecular weight polymeric cationic coagulant / flocculant, the high molecular weight polymeric cationic coagulant / flocculant having an average molecular weight (M) of 100,000 to 2,000,000 Da. w In some embodiments, the high molecular weight polymeric cationic coagulant / flocculant has an average net charge of 10 to 1,000.

[0293] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is a low molecular weight polymeric cationic coagulant / flocculant, the low molecular weight polymeric cationic coagulant / flocculant having an average molecular weight (M) of 10,000 to 100,000 Da. w In some embodiments, the low molecular weight polymeric cationic coagulant / flocculant has a net charge of 3-10.

[0294] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is a high molecular weight polymeric anionic coagulant / flocculant and the high molecular weight polymeric cationic coagulant / flocculant has a molecular weight between 100,000 and 2,000,000. In some other embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is a low molecular weight polymeric anionic coagulant / flocculant and the low molecular weight polymeric anionic coagulant / flocculant has a molecular weight between 10,000 and 100,000.

[0295] In some embodiments, the high molecular weight polymeric anionic coagulant / flocculant has a net charge between 10 and 1,000. In some other embodiments, the low molecular weight polymeric anionic coagulant / flocculant has a net charge between 3 and 10.

[0296] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is a high molecular weight polymeric coagulant / flocculant, and the high molecular weight polymeric nonionic coagulant / flocculant has a molecular weight of 100,000 to 2,000,000.

[0297] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water clarifier is a low molecular weight polymeric coagulant / flocculant, and the low molecular weight polymeric non-ionic coagulant / flocculant has a molecular weight of 10,000 to 100,000.

[0298] In some embodiments, reverse emulsion breaking compositions comprise one or more multiply charged cationic or anionic compounds, one or more emulsion breakers, and one or more diluents.

[0299] In some embodiments, the method further includes separating oil and solids from water in the treated production fluid via filtration, sedimentation, desalting, electrochemical techniques, centrifugation, flotation, or combinations thereof.

[0300] In some embodiments, the REB compositions or multiply charged cationic or anionic compounds disclosed herein can break oil-in-water emulsions in a production fluid, as shown by conventional bottle tests as described in the Examples section of this disclosure, when the production fluid has a concentration of a charge cationic or anionic compound or mixture thereof of about 1 ppm to about 200 ppm, about 10 to about 200 ppm, about 10 ppm to about 150 ppm, about 10 ppm to about 75 ppm, about 10 ppm to about 100 ppm, about 10 ppm to about 120 ppm, about 200 ppm, about 180 ppm, about 160 ppm, about 140 ppm, about 120 ppm, about 100 ppm, about 80, about 60 ppm, about 50 ppm, about 40 ppm, or any value therebetween, after administration of the multiply charged cationic or anionic compound or mixture thereof, or the REB composition.

[0301] As used herein, the term "substantially free" or "free" refers to a composition that is completely devoid of the component or has such a small amount of the component that it does not affect the performance of the composition. The component may be present as an impurity or contaminant and should be less than about 0.5% by weight. In another embodiment, the amount of the component is less than about 0.1% by weight, and in yet another embodiment, the amount of the component is less than about 0.01% by weight.

[0302] The terms "weight percent," "wt%," "percent by weight," "% by weight," and variations thereof, as used herein, refer to the concentration of a substance by dividing the weight of that substance by the total weight of the composition and multiplying by 100. As used herein, it is understood that "percent," "%," and the like are intended to be synonymous with "weight percent," "% by weight," and the like.

[0303] The disclosed methods and compositions may comprise, consist essentially of, or consist of the components and ingredients of the disclosed compositions or methods, as well as other components described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, or ingredients only if the additional steps, components, or ingredients do not materially alter the basic and novel characteristics of the methods and compositions as claimed. EXAMPLES

[0304] The embodiments of the present disclosure are further defined in the following non-limiting examples. Although these examples show certain embodiments of the present disclosure, they are provided merely as examples. From the above discussion and these examples, those skilled in the art can ascertain the essential features of the present disclosure, and can make various changes and modifications to the embodiments of the present disclosure to adapt it to various usages and conditions without departing from the spirit and scope thereof. Thus, various modifications of the embodiments of the present disclosure will be apparent to those skilled in the art from the foregoing description, in addition to those shown and described herein. Such modifications are also intended to fall within the scope of the appended claims.

[0305] Example 1 Synthesis of multiply charged cationic compound 1 (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 96 grams) and water (20 grams) were charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Tetraethylenepentamine (TEPA, 12 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The progress of the reaction was monitored for monomer consumption by ESI-MS and / or NMR spectroscopy. The resulting aqueous solution of compound 1 was used as is for its application testing as a REB.

[0306] Example 2 Synthesis of multiply charged cationic compound 2 Ethyleneamine E-100 from Huntsman was used in this reaction. E-100 is a mixture of tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexaethyleneheptamine (HEHA), and other high molecular weight amines. E-100 has a number average molecular weight (M) of 250-300 g / mol. n ) is a complex mixture of various linear, cyclic, and branched amines.

[0307] (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 60 grams) and water (20 grams) were charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Ethyleneamine E-100 (12 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The resulting aqueous solution of compound 2 was used as is for application testing.

[0308] Example 3 Synthesis of multiply charged cationic compound 3 (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 70 grams) and water (20 grams) were charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Pentaethylenehexamine (PEHA, 10 grams, 99%) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The resulting aqueous solution of compound 3 was used as is for application testing.

[0309] Example 4 Synthesis of multiply charged cationic compound 4 (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 130 grams) and water (20 grams) were charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Diethylenetriamine (DETA, 10 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was increased to 80° C. and stirred overnight or until the APTAC was consumed at more than 98%. The reaction temperature was increased to 80° C. and stirred overnight or until the APTAC was consumed at more than 98%. The resulting aqueous solution of compound 4 was used as is for application testing.

[0310] Example 5 Synthesis of multiply charged cationic compound 5 BASF Lupasol G20 (weight average molecular weight (Mw ) A 50% aqueous solution of polyethyleneimine having approximately 1,300 g / mol) was used in this reaction.

[0311] (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 78.55 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Lupasol G20 (50%, 50 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The resulting aqueous solution of compound 5 was used as is for application testing.

[0312] Example 6 Synthesis of multiply charged cationic compound 6 BASF Lupasol G100 (weight average molecular weight (M w ) A 50% aqueous solution of polyethyleneimine having approximately 5000 g / mol) was used for this reaction.

[0313] (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 72.4 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Lupasol G100 (50%, 50 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The resulting aqueous solution of compound 6 was used as is for application testing.

[0314] Example 7 Efficacy of some exemplary multiply charged cationic polyamines to break emulsions in production streams The effectiveness of several exemplary multiply charged cationic compounds was tested using production fluids from three different sites. Sample IDs and structures of the exemplary multiply charged cationic compounds are listed in Table 2. [Table 3]

[0315] The effectiveness of REBs is typically measured by emulsion stability of production fluids spiked with specific concentrations of REBs under simulated conditions that closely match the production site.

[0316] Emulsion stability is monitored by measuring phase separation up to 90°C using a conventional bottle test. The production fluid, e.g., emulsion solution (100 mL), is poured into a 6 oz. glass prescription bottle and heated in a water bath to the target system temperature. Diluent is usually added to the emulsion at some point in the process and mixed using a mechanical shaker at low speed for 5 minutes or by shaking the bottle by hand.

[0317] The bottle tests were performed using a high temperature bottle test instrument. This bottle test instrument is capable of achieving high temperature and pressure conditions that match conventional methods for oil / water separation at any particular production site. The bottle test instrument is a very simple processing system and does not exactly replicate what occurs within a complex processing system that uses separators, wash tanks, heater treaters, etc. at an oil production facility, but it does allow for the test results to be compared to those at the facility. For example, if the oil leaving the processing system contains only 0.5% BS&W (bitumen, solids, and water emulsion), the oil analysis from the bottle test for REB should be close to this result.

[0318] There are no standard bottle test conditions because each customer's equipment, its placement, distance, temperature, and chemical injection points are different. However, the bottle test equipment used in this example can be adjusted for chemical ratios, agitation, temperature, and settling time to suit the conditions of the production facility.

[0319] Production fluids were collected from a customer process for use in this example. Some degradation of the samples occurs over time, but in this work the time to bottle and start testing was minimized to reduce variability in results. Diluent samples were collected and used over multiple days.

[0320] For the bottle test, approximately 100 ml of sample was added to the bottle. EB was then injected into the bottle (rate based on oil cut), the bottle was sealed and placed in the bottle test instrument. The sample was then heated to a temperature such as 140° C., and the bottle was agitated using a mechanical shaker. REB and diluent were injected into the bottle and various agitation stages were completed. Water drop readings were taken over a set time period, recorded in mL, and then a sample of the top oil was taken at the test temperature and pressure using a syringe. This oil sample was added to a centrifuge tube containing xylene, toluene, or light oil (e.g., Varsol™). The mixture was shaken well to mix and then centrifuged. The BS&W was then measured. Water quality was tested using a variety of techniques including visual inspection and turbidity. Typically, the composite sample was measured for emulsion by removing the free water, gently mixing, and then transferring to a centrifuge tube with xylene, toluene, or light oil (e.g., Varsol™). The samples were shaken well to mix well, then centrifuged and the BS&W recorded.

[0321] Water clarity was ranked on a comparative appearance scale of 11 (partially reversed) to 1 (approximately 50 NTU). A rating of 9 can be considered equivalent to 1500 NTU, and a rating of 4 or 5 is equivalent to approximately 500 NTU.

[0322] Test results for exemplary multiply charged polyamines and several existing REBs are shown in Tables 4, 5, and 6A-6B for three different field tests, respectively. In Tables 4, 5, and 6A-6B, G=Good, F=Fair, P=Poor, VP=Very Poor. "+" or "-" are additional modifiers for "G," "P," and "VP." [Table 4] [Table 5] [Table 6] [Table 7] [Table 8]

[0323] Example 8 Synthesis of multiply charged cationic compound 7 (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 100 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Triethylenetetramine (TETA, 60%, 15 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The resulting aqueous solution of compound 7 was used as is for application testing.

[0324] Example 9 Synthesis of multiply charged cationic compound 8 (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 216 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Tris(2-aminoethyl)amine (95%, 216 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The resulting aqueous solution of compound 8 was used as is for application testing.

[0325] Example 10 Synthesis of multiply charged cationic compound 9 (3-Acrylamidepropyl)trimethylammonium chloride (APTAC, 75%, 199 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Ethylenediamine (EDA, 99%, 11 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of APTAC exceeded 98%. The resulting aqueous solution of compound 9 was used as is for application testing.

[0326] Example 11 Synthesis of multiply charged cationic compounds 10 2-Acrylamido-2-methylpropanesulfonic acid sodium salt (NaAMPS, 58%, 94 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Diethylenediamine (DETA, 99%, 5 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was increased to 80° C. and stirred overnight or until the consumption of NaAMPS exceeded 98%. The resulting aqueous solution of compound 10 was used as is for application testing.

[0327] Example 12 Synthesis of multiply charged cationic compound 11 2-Acrylamido-2-methylpropanesulfonic acid sodium salt (NaAMPS, 58%, 70 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Triethylenepentamine (TEPA, 99%, 5 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of NaAMPS exceeded 98%. The resulting aqueous solution of compound 11 was used as is for application testing.

[0328] Example 13 Synthesis of multiply charged cationic compound 12 2-Acrylamido-2-methylpropanesulfonic acid sodium salt (NaAMPS, 58%, 50 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Ethylenediamine (99%, 50 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was increased to 80° C. and stirred overnight or until the consumption of NaAMPS exceeded 98%. The resulting aqueous solution of compound 12 was used as is for application testing.

[0329] Example 14 Synthesis of multiply charged cationic compound 13 2-Acrylamido-2-methylpropanesulfonic acid sodium salt (NaAMPS, 58%, 9.5 grams) was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Tris(2-aminoethyl)amine (95%, 145 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of NaAMPS exceeded 98%. The resulting aqueous solution of compound 13 was used as is for application testing.

[0330] Example 15 Synthesis of multiply charged cationic compound 14 Vinylsulfonic acid sodium salt (NaVS, 25%, 152 grams) solution was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Diethylenediamine (99%, 6 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was raised to 80° C. and stirred overnight or until the consumption of NaVS exceeded 98%. The resulting aqueous solution of compound 14 was used as is for application testing.

[0331] Example 16 Synthesis of multiply charged cationic compound 15 Vinylsulfonic acid sodium salt (NaVS, 25%, 113 grams) solution was charged into a 250 mL three-neck RBF equipped with a magnetic stir bar, temperature probe, and condenser. Ethyleneamine E-100 (99%, 9 grams) was then added to the well-stirred reaction mixture at room temperature. The reaction temperature was increased to 80° C. and stirred overnight or until the consumption of NaVS exceeded 98%. The resulting aqueous solution of compound 15 was used as is for application testing.

[0332] The disclosure being thus described, it will be apparent that the same may be varied in many ways. Such variations are not to be regarded as departures from the spirit and scope of the disclosure, and all such modifications are intended to be included within the scope of the following claims.

Claims

1. Compounds derived from an aza-Michael addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) bearing an ionic group according to one of the following formulas: 【Chemistry 1】 During the ceremony, X is NH or O; R ２ But, H, CH ３ or unsubstituted linear or branched C ２ ~C １０ an alkyl, alkenyl, or alkynyl group; R ２’ But, H, CH ３ or unsubstituted or substituted linear or branched chain C １ ~C １０ Alkyl, alkenyl, alkynyl groups, -COOH, -CH ２ COOH, Y', or -(CH ２ ) ｍ -Y', m is an integer from 2 to 4, R3 is absent or is an unsubstituted straight or branched chain C １ ~C ３０ is an alkylene group, Y is -NR ４ R ５ R ６ （＋） Wherein R ４ , R ５ , and R ６ became independent and C １ ~C １０ is an alkyl group, Y' is -COOH, -SO ３ H, -PO ３ H, -OSO ３ H, -OPO ３ H, or a salt thereof; The compound is a multiply charged cationic compound having two or more positive charges, or a multiply charged anionic compound having two or more negative charges.

2. The polyamine is NH ２ - [R １０’ ] ｎ -NH ２ , (RNH) ｎ -RNH ２ , H ２ N-(RNH) ｎ -RNH ２ , or H ２ N-(RN(R')) ｎ -RNH ２ A linear, branched, or dendritic polyamine having the general formula: １０’ is a linear or branched unsubstituted or substituted C ２ ~C １０ alkylene groups, or combinations thereof, where R is -CH ２ --, --CH ２ CH ２ --, --CH ２ CH ２ CH ２ -, -CH(CH ３ ) CH ２ -, linear or branched unsubstituted or substituted C ４ ~C １０ alkylene groups, or combinations thereof, where R' is -CH ２ --, --CH ２ CH ２ --, --CH ２ CH ２ CH ２ -, -CH(CH ３ ) CH ２ -, linear or branched unsubstituted or substituted C ４ ~C １０ Alkyl group, RNH ２ , R.N.H.R.N.H. ２ , or RN(RNH ２ ) ２ and n is from 2 to 1,000,000.

3. 3. The compound of claim 1 or 2, wherein the polyamine is (i) an unmodified polyamine, (ii) a modified polyamine, (iii) an ethoxylated polyamine, a propylated polyamine, a polyquat-bearing polyamine, a polyglycerol-bearing polyamine, or a combination thereof, or (iv) a linear, branched, or dendritic polyethyleneimine.

4. 4. The compound of claim 1, wherein the polyamine comprises: (i) only primary and secondary amine groups; (ii) only primary, secondary, and tertiary amine groups; or (iii) only primary and tertiary amine groups.

5. The polyamine is (i) NH ２ - [R １０’ ] ｎ -NH ２ (In the formula, R １０’ is a linear or branched unsubstituted or substituted C ２ ~C １０ (ii) (RNH), ｎ -RNH ２ Or H ２ N-(RNH) ｎ -RNH ２ (Wherein, R is —CH ２ --, --CH ２ CH ２ --, --CH ２ CH ２ CH ２ -, -CH(CH ３ ) CH ２ -, linear or branched unsubstituted or substituted C ４ ~C １０ alkylene groups, or combinations thereof), or (iii) H ２ N-(RN(R')) ｎ -RNH ２ (Wherein, R is —CH ２ --, --CH ２ CH ２ --, --CH ２ CH ２ CH ２ -, -CH(CH ３ ) CH ２ -, linear or branched unsubstituted or substituted C ４ ~C １０ alkylene groups, or combinations thereof, where R' is -CH ２ --, --CH ２ CH ２ --, --CH ２ CH ２ CH ２ -, -CH(CH ３ ) CH ２ -, linear or branched unsubstituted or substituted C ４ ~C １０ Alkyl group, RNH ２ , R.N.H.R.N.H. ２ , or RN(RNH ２ ) ２ 5. The compound according to claim 1, which is a polyamine having the general formula:

6. The activated olefin is (i) (3-acrylamidopropyl)trimethylammonium chloride (APTAC) or [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), (ii) (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt (DM 6. The compound of claim 1, which is selected from the group consisting of 2-(methacryloyloxy)-N,N,N-trimethylethane-1-aminium methyl sulfate (DMAEA-MSQ), 2-(acryloyloxy)-N,N,N-trimethylethaneaminium chloride (DMAEA-MSQ), and (iii) acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), itaconic acid, maleic acid, 3-(allyloxy)-2-hydroxypropane-1-sulfonate, vinylsulfonic acid, vinylphosphonic acid, or mixtures thereof.

7. The polyamine has an average molecular weight (M) of about 60 to about 2,000,000 Da, or about 60 to about 5,000 Da. ｗ 7. The compound according to claim 1, wherein

8. 8. The compound according to any one of claims 1 to 7, wherein the compound is (i) a single molecule, (ii) a mixture of at least two multiply charged cationic compounds or at least two multiply charged anionic compounds, (iii) a mixture of at least two multiply charged cationic compounds or at least two multiply charged anionic compounds derived from the same polyamine and the activated olefin, or (iv) a mixture of at least two multiply charged cationic compounds or at least two multiply charged anionic compounds derived from different polyamines and the same activated olefin.

9. The compound according to any one of claims 1 to 8, wherein the compound has an average molecular weight of from about 100 to about 2,000,000 Da, or from about 100 to about 5,500 Da.

10. 10. The compound of any one of claims 1 to 9, wherein the compound has (i) at least 10, 15, 20, or 30 positive charges, (ii) at least 4, 5, 6, 7, or 8 positive charges, (iii) at least 10, 15, 20, or 30 negative charges, or (iv) at least 4, 5, 6, 7, or 8 negative charges.

11. The compound is 【Chemistry 2】 wherein n=0-1000.

12. The compound is 【Chemistry 3】 2. The compound of claim 1, wherein the compound is one or more of:

13. The compound is derived from polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC), the polyethyleneimine being linear PEI and having an average molecular weight (M ｗ 2. The compound of claim 1 having the formula:

14. The compound is derived from polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC), the polyethyleneimine being linear PEI and having an average molecular weight (M ｗ 2. The compound of claim 1 having the formula:

15. The compound is derived from polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC), the polyethyleneimine being a branched chain PEI with an average molecular weight (M ｗ 2. The compound of claim 1 having the formula:

16. The compound according to any one of claims 1 to 15, wherein the compound is water soluble.

17. 1. A method for synthesizing a compound, comprising: contacting an activated olefin having a cationic group with a polyamine to produce a compound; The activated olefin is according to one of the following formulas: 【Chemistry 4】 During the ceremony, X is NH or O; R ２ But, H, CH ３ or unsubstituted linear or branched C ２ ~C １０ an alkyl, alkenyl, or alkynyl group; R ２’ But, H, CH ３ or unsubstituted or substituted linear or branched chain C １ ~C １０ Alkyl, alkenyl, alkynyl groups, -COOH, -CH ２ COOH, Y', or -(CH ２ ) ｍ -Y', m is an integer from 2 to 4, R ３ is absent or unsubstituted linear or branched chain C １ ~C ３０ is an alkylene group, Y is -NR ４ R ５ R ６ （＋） and Y' is -COOH, -SO ３ H, -PO ３ H, -OSO ３ H, -OPO ３ H, or a salt thereof; R ４ , R ５ , and R ６ became independent and C １ ~C １０ is an alkyl group, A process wherein the polyamine and activated olefin undergo an aza-Michael addition reaction, and the compound is as claimed in any one of claims 1 to 16.

18. 20. The method of claim 17, wherein the contacting step is carried out in the presence of a reaction solvent, a reaction solvent and an alkaline source, a reaction solvent and an acid, or a reaction solvent and a catalyst.

19. 20. The method of claim 18, wherein the reaction solvent is water, methanol, ethanol, propanol, glycol, PEG, or a mixture thereof.

20. 20. The method of claim 18, wherein the contacting step is carried out in the presence of benzyltrimethylammonium hydroxide.

21. 20. The method of claim 18, wherein the contacting step is carried out in the absence of an acid, a base, an alkaline source, or a catalyst.

22. An article, product, or composition comprising one or more compounds according to any one of claims 1 to 16.

23. 23. The article, product, or composition of claim 22, wherein the article, product, or composition further comprises a carrier.

24. 24. The article, product, or composition of claim 22 or 23, wherein the article, product, or composition is a water-based article, product, or composition.

25. 24. The article, product, or composition of claim 22 or 23, wherein the carrier is water, an alcohol, an alkylene glycol, an alkylene glycol alkyl ether, or a combination thereof.

26. 26. The article, product, or composition of any one of claims 22-25, further comprising an additional surfactant, said additional surfactant being a nonionic, semi-nonionic, cationic, anionic, amphoteric, zwitterionic, gemini, surfactant, or mixtures thereof.

27. 1. A method for breaking inverse emulsions in production fluids from an oil and gas production system, comprising: contacting a production fluid of an oil production system with an inverse emulsion breaking (REB) composition to generate a treated production fluid; The reverse emulsion breaking composition comprises one or more compounds or salts thereof according to any one of claims 1 to 16, and one or more additional inverse emulsion breaking composition agents.

28. 30. The method of claim 27, wherein the inverse emulsion breaking composition breaks an oil-in-water emulsion in the production fluid.

29. 29. The method of claim 27 or 28, wherein the production fluid comprises an oil-in-water emulsion, a water-in-oil-in-water emulsion, or both.

30. 29. The method of claim 27 or 28, wherein the production fluid (i) comprises crude oil, refined oil, bitumen, condensate, waste oil, distillate, fuel, or a mixture thereof; (ii) is from a steam-assisted gravity drainage (SAGD) process, the production fluid comprises bitumen and water; or (iii) is produced water, the produced water being the water portion of the production fluid after oil and dirt have been removed.

31. 31. The method of any one of claims 27 to 30, wherein the compound has an average net charge of 3 to 100, or 3 to 15.

32. 32. The method of any one of claims 27-31, wherein the REB composition further comprises a carrier, and the carrier is water, an alcohol, an alkylene glycol, an alkylene glycol alkyl ether, or a combination thereof.

33. 33. The method of claim 32, wherein the carrier is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

34. 34. The method of any one of claims 27-33, wherein the REB composition further comprises one or more additional reverse emulsion breaking agents.

35. The method of any one of claims 27 to 34, wherein the REB composition comprises from about 30% to about 70% by weight of the compound or salt thereof.

36. 36. The method of any one of claims 27 to 35, wherein the compound has a concentration of about 0.5 ppm to about 100 ppm or about 5 ppm to about 60 ppm in the treated production fluid after the REB composition is applied to the production fluid.

37. 37. The method of any one of claims 27 to 36, wherein the method further comprises contacting the production fluid with an emulsion breaker or an additional inverse emulsion breaking (REB) agent, wherein the emulsion breaker or the additional REB agent are contacted with the production fluid independently, simultaneously or sequentially.

38. 38. The method of claim 37, wherein the emulsion breaker or the additional REB agent is contacted with the production fluid by a compound in the REB composition or via a separate composition.

39. The additional REB agent is 【Chemistry 5】 A terpolymer having an average molecular weight of about 20,000 to about 20,000,000 Da, comprising monomers of the formula: R ３１ , R ３２ , and R ３３ are independently hydrogen or alkyl; R ３４ , R ３５ , R ３６ , R ３７ , and R ３８ The method of claim 37 or 38, wherein is independently alkyl, p is an integer from 1 to 6, and m, n, and o are integers.

40. 39. The method of claim 37 or 38, wherein the emulsion breaker or the additional REB agent is another polymeric cationic, anionic, nonionic, inorganic coagulant / flocculant, or an oxyalkylated phenol-formaldehyde resin, a resin ester, an oxyalkylated polyalkylamine, a polyol, a crosslinked polyol with a di- or polyfunctional crosslinker, an isocyanate, an acid, or a combination thereof.

41. 39. The method of claim 37 or 38, wherein the emulsion breaker or the additional REB agent comprises dendritic polyamines, dendritic polyamidoamines, hyperbranched polyethyleneimines, their reaction products with gluconolactone, alkylene oxides, 3-chloro-2-hydroxypropanesulfonic acid, alkyl halides, benzyl halides, and dialkyl sulfates, or mixtures thereof.

42. 39. The method of claim 37 or 38, wherein the emulsion breaker or the additional REB agent comprises a polyepihalohydrin, a polyelectrolyte thereof, tridithiocarbamic acid, a dithiocarbamic acid salt, a dimethylaminoethyl acrylate methyl chloride, a benzyl chloride quaternary salt, a polymeric quaternary ammonium betaine, a metal salt, zinc chloride, aluminum chloride, a polymeric quaternary ammonium salt, a copolymer of acrylic acid and acrylamide, or a mixture thereof.

43. The emulsion breaker or the additional REB agent is a high molecular weight polymeric cationic coagulant / flocculant, and the high molecular weight polymeric cationic coagulant / flocculant has an average molecular weight (M ｗ 39. The method of claim 37 or 38, wherein the high molecular weight polymeric cationic coagulant / flocculant has an average net charge of 10 to 1,000.

44. 39. The method of claim 37 or 38, wherein the emulsion breaker or the additional REB agent is a low molecular weight polycationic coagulant / flocculant, the low molecular weight polycationic coagulant / flocculant having an average molecular weight of 10,000 to 100,000 Da, and the low molecular weight polycationic coagulant / flocculant having a net charge of 3 to 10.

45. 39. The method of claim 37 or 38, wherein the emulsion breaker or the additional REB agent is a high molecular weight, polymeric anionic coagulant / flocculant, the high molecular weight, polymeric cationic coagulant / flocculant having a molecular weight of 100,000 to 2,000,000, and the high molecular weight, polymeric anionic coagulant / flocculant having a net charge of 10 to 1,000.

46. 39. The method of claim 37 or 38, wherein the emulsion breaker or the additional REB agent is a low molecular weight polyanionic coagulant / flocculant, the low molecular weight polycationic coagulant / flocculant having a molecular weight of 10,000 to 100,000, and the low molecular weight polyanionic coagulant / flocculant having a net charge of 3 to 10.

47. 39. The method of claim 37 or 38, wherein the emulsion breaker or the additional REB agent is a high molecular weight polymeric non-ionic coagulant / flocculant, the high molecular weight polymeric non-ionic coagulant / flocculant having a molecular weight of 100,000 to 2,000,000, or a low molecular weight polymeric non-ionic coagulant / flocculant, the low molecular weight polymeric non-ionic coagulant / flocculant having a molecular weight of 10,000 to 100,000.

48. 48. The method of any one of claims 27 to 47, wherein the reverse emulsion breaking composition further comprises a diluent.

49. 48. The method of any one of claims 27-47, wherein the method further comprises separating oil and solids from water in the treated production fluid via filtration, sedimentation, desalting, electrochemical techniques, centrifugation, flotation, or combinations thereof.

50. 17. A reverse emulsion breaking composition comprising a compound according to any one of claims 1 to 16 or a salt thereof and one or more additional reverse emulsion breaking composition agents.

51. 51. The reverse emulsion breaking composition of claim 50, wherein the reverse emulsion breaking composition breaks an oil-in-water emulsion in the production fluid.

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