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 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), methods of making the same, and use thereof; and methods of using the multiple charged cationic or anionic compounds in a reverse emulsion breaker composition to break reverse emulsion commonly found in a produced fluid in oil and gas operations.SOLUTION: An activated olefin (Michael acceptor) has an ionic group according to one of the formulas (I), (II) and (III) in the figure, where 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(e) to Provisional Application No. 62 / 724,398, filed on August 29, 2018, the entire disclosure of which is hereby incorporated by reference herein.

[0002] The present invention generally relates to the field of multiply - charged cationic or anionic compounds, methods of making them, and their use. The present disclosure also generally relates to the field of use of inverse emulsion breaking compositions in oil and gas operations. In particular, the present disclosure relates to a new 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 use. The disclosed multiply - charged cationic or anionic compounds or their salts have at least two or three positive or negative charges within each molecule. The present disclosure also relates to using an inverse emulsion breaking composition comprising one or more of the multiply - charged cationic or anionic compounds disclosed herein to break water - in - oil emulsions or complex emulsions in production fluids in oil and gas operations. The methods, inverse emulsion breaking compositions, and multiply - charged cationic or anionic compounds disclosed herein are more effective at separating water from oil than the methods, compositions, or compounds currently used in oil and gas operations.

Background Art

[0003] Water - in - oil and water - in - oil - in - water emulsions can occur in many industrial systems. For example, production fluids containing emulsified oil, such as inverse emulsions or water - in - oil 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 and to create water-in-oil and oil-in-water emulsions. These emulsions contain bitumen and water and need to be broken, and the bitumen is sent for upgrading / refining, while the accompanying water (separated from the emulsion) is treated and reused as feed water for the steam generator.

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

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

[0007] However, the desired separation of oil / hydrocarbons and water for water-in-oil emulsions or complex emulsions can be difficult with physical processes alone due to the nature of the emulsions. In such situations, demulsifying coagulants and flocculants, such as inverse emulsion breakers, can be used to break the emulsion and accelerate the agglomeration of oil particles. Inorganic coagulants have been used alone or in combination with organic polyelectrolytes for the demulsification of 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 liquid cyclones, flotation tanks, filtration units, and centrifuges. The performance of these devices can be significantly improved using chemical inverse emulsion breakers. Inverse emulsion breakers are alternatively called deoiling agents (by removal of oil) or water clarifying agents (by improvement of water quality).

[0009] Furthermore, emulsion droplets that were not removed by the primary separation system would be significantly stabilized from further coalescence by two mechanisms. The first is the mutual charge repulsion of the emulsion droplets. When the fluid is processed, the pH of the water increases due to the pressure drop, and as a result, the naturally occurring fatty acids and naphthenic acids present in the crude oil are deprotonated. These salts provide a negative charge to the emulsion surface and repel other oil droplets that would coalesce upon interaction.

[0010] The second is the organic and / or inorganic solids adsorbed on the emulsion oil / water interface, which effectively seal the interface from exposure to other emulsion droplets and interfere with the coalescence mechanism. When 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 are formed, creating a solid phase at the water interface and further slowing down coalescence.

[0011] Effective deoiling can be achieved using polyelectrolytes that promote the aggregation of emulsion droplets into larger aggregates, which can then be more easily acted upon by physical separation equipment in the water treatment process. Polyelectrolytes can neutralize the repulsive charges expressed on the emulsion droplets and, if of sufficient size, can also bridge between the droplets and bring them together into clusters where coalescence can occur due to proximity. Inverse emulsion breakers are designed to function in the high-salinity brines common in production fluids.

[0012] Regarding more effective and efficient oil / hydrocarbon separation processes, various chemicals as inverse emulsion breakers have been invented or investigated. The chemicals tried include various cationic polymers or molecules. However, better inverse emulsion breakers are still needed because the existing ones are insufficient.

[0013] Quaternary ammonium compounds have been used for many years as reverse 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 mainly consist of two parts, a hydrophobic group, such as a long alkyl group, and a quaternary ammonium base. The unique positive charge of ammonium plays an important role, for example, in electrostatic interactions between the surfactant and the surface or on the surface of emulsion droplets. However, quaternary ammonium compounds used for such purposes are often bisquaternary species or species quaternized with benzyl chloride and are known to be very harmful. In addition, there are government regulations for releasing any water containing a single quaternary compound into the environment.

Summary of the Invention

Problems to be Solved by the Invention

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

[0015] Therefore, it is an object to develop a new reverse emulsion breaker having improved properties with improved oil / hydrocarbon and water separation characteristics.

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

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

[0018] An object of the present disclosure is also to develop a new reverse emulsion breaker having improved oil / hydrocarbon and water separation characteristics.

[0019] A further object of the present disclosure is to develop methods and corresponding inverse emulsion breaking compositions for more efficiently and effectively separating 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, together with the claims set forth herein.

Means for Solving the Problems

[0021] This specification discloses novel compounds, methods for making the disclosed compounds, and articles, products, or compositions containing the disclosed compounds. More specifically, this specification discloses multiply charged cationic or anionic compounds containing a large number of positive or negative charges within a single molecule of various molecular sizes and derived from water-soluble polyamines.

[0022] This specification also discloses 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 water-in-oil or complex 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 compared 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 used as flocculants, water purifying agents, corrosion inhibitors, clay stabilizers, and antibacterial agents in aqueous 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 use, cost, and operational complexity.

[0024] In one aspect, the present specification discloses a compound derived from an aza-Michael addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) having an ionic group represented by one of the following formulas:

Chemical formula

[0025] In another aspect, the present specification discloses a method for preparing a compound or a salt thereof, the method comprising contacting a polyamine with an activated olefin (Michael acceptor) having an ionic group represented by one of the following formulas:

Chemical formula

[0026] In yet another aspect, an article, product, or composition comprising one or more of the compounds disclosed herein is provided herein.

[0027] In yet another aspect, a composition for decomposing an inverse emulsion in a production fluid from an oil and gas production system is disclosed herein, wherein the inverse emulsion breaking composition comprises one or more of the compounds disclosed herein and one or more additional inverse emulsion breaking composition agents. In some embodiments, the inverse emulsion composition disclosed herein breaks an oil-in-water emulsion in the production fluid.

[0028] In another aspect, the present specification discloses a method for decomposing inverse emulsions in production fluids from oil and gas production systems, the method comprising contacting the production fluid of the oil and gas production system with an inverse emulsion breaker (REB) composition to produce 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 composition disclosed herein breaks water-in-oil emulsions in the production fluid.

[0029] The above summary is merely exemplary 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 illustrate and describe exemplary embodiments of the present technology. Accordingly, the drawings and detailed description are also not intended to be limiting and should be regarded as essentially exemplary.

Brief Description of the Drawings

[0030]

Figure 1

Figure 2

[0031] Various embodiments of the present disclosure will be described in detail with reference to the drawings, with like reference numerals representing like components throughout several figures. References to various embodiments are not intended to limit the scope of the present disclosure. The figures presented herein are not limitations on the various embodiments according to the present disclosure, but are presented for illustrative explanation of the present disclosure.

Best Mode for Carrying Out the Invention

[0032] In the following embodiments for carrying out the invention, reference can be made to the accompanying drawings, schemes, and structures that form part of this specification. In the drawings, unless otherwise indicated by context, typically the same reference symbols are recognized as representing the same components. The exemplary embodiments described in the embodiments for carrying out the invention, the drawings, and the claims are not meant to be limiting. Other embodiments can be utilized and other changes can 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 a particular embodiment is not intended as an exhaustive description or as a limitation to a broader aspect discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced in any other embodiment(s).

[0034] This specification discloses methods and compositions for decomposing 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 decomposing inverse emulsions 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 a polyamine and an activated olefin.

[0035] Embodiments of the present disclosure are not limited to any particular composition and method, which can be varied and will be understood by those skilled in the art. It should be further understood that all technical terms used herein are for the purpose of merely describing particular embodiments and are not intended to be limiting in any way or scope. For example, as used in this specification and the appended claims, the singular forms "a", "an", and "the" may include plural referents unless the context clearly dictates otherwise. Further, all units, prefixes, and symbols may be expressed in their SI certified forms.

[0036] The numerical ranges recited herein include numbers within the defined ranges. Throughout the present disclosure, various aspects of the disclosure are presented in a range format. The description in range format is for convenience and brevity only and should not be construed as an immutable limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges within that range as well as individual numerical values (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0037] To make the present disclosure more readily understandable, certain terms will first be defined. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art related to the embodiments of the present disclosure. Many methods and materials similar to, modified from, or equivalent to those described herein can be used in the practice of the embodiments of the present disclosure without undue experimentation, and the preferred materials and methods are described herein. In the description and claims of the embodiments of the present disclosure, the following technical terms will be used according to the definitions set forth below.

[0038] As used herein, the term "about" refers to a variation in quantity that can occur, for example, due to typical measurements and liquid handling procedures used in making concentrates or use solutions in the real world, errors in these procedures, differences in the manufacture, source, or purity of the components used in making the composition or performing the method. The term "about" also encompasses amounts that vary due to new equilibrium conditions for the composition obtained from a particular initial mixture. Whether or not modified by the term "about", the claims include the equivalents of that 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 bonds to non-hydrogen or non-carbon atoms. Substituents also include groups in which one or more carbon atoms (s) or hydrogen atoms (s) are replaced by one or more bonds including double or triple bonds to heteroatoms. 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 by 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, including 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 a substituent that replaces one or more hydrogens of 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, phosphonate, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamide, nitro, trifluoromethyl, cyano, azide, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

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

[0044] An alkenyl group or alkene is a straight-chain, branched-chain, or cyclic alkyl group having 2 to about 30 carbon atoms and further including at least one double bond. In some embodiments, the alkenyl group has 2 to about 30 carbon atoms, or typically 2 to 10 carbon atoms. The alkenyl group may be substituted or unsubstituted. In the case of the double bond of the alkenyl group, the configuration of the double bond may be a trans or cis configuration. The alkenyl group may be substituted in the same manner as the alkyl group.

[0045] An alkynyl group is a straight-chain, branched-chain, or cyclic alkyl group having 2 to about 30 carbon atoms and further including at least one triple bond. In some embodiments, the alkynyl group has 2 to about 30 carbon atoms, or typically 2 to 10 carbon atoms. The alkynyl group may be substituted or unsubstituted. The alkynyl group may be substituted in the same manner as the alkyl or alkenyl group.

[0046] As used herein, the terms "alkylene", "cycloalkylene", "alkynylidene", and "alkenylene" each, alone or as part of another substituent, refer to a divalent radical derived from an alkyl, cycloalkyl, or alkenyl group, such as exemplified by -CH2CH2CH2-. For alkylene, cycloalkylene, alkynylene, and alkenylene groups, the orientation of the linking group is not implied.

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

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

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

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

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

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

[0053] As used herein, the term "solvent" refers to any inorganic or organic solvent. The solvent is useful in the disclosed methods or compositions as a reaction solvent or a carrier solvent. 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. The solvent used herein can be a single solvent or a mixture of many different solvents.

[0054] Examples of 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, or mixtures thereof.

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

[0056] Generally, when used in the present disclosure, the acid includes both organic acids and inorganic acids. Examples of 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. Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid are also included as organic acids. Combinations of these organic acids can also be used. Examples of 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. The inorganic acid can be used alone, in combination with other inorganic acid(s), or in combination with one or more organic acids. The acid generator includes, for example, generators such as potassium fluoride, sodium fluoride, lithium fluoride, ammonium fluoride, ammonium bifluoride, sodium fluorosilicate, and can be used to form a suitable acid.

[0057] Examples of acids particularly suitable in the methods or compositions disclosed herein include inorganic acids 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] Peroxycarboxylic acid and peroxocarboxylic 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 will be understood by those skilled in the art, a peracid refers to an acid in which the hydrogen of the hydroxyl group in a carboxylic acid is replaced by a hydroxyl group. An oxidizing peracid may sometimes be referred to herein as a peroxycarboxylic acid.

[0059] Peracids include any compound of the formula R--(COOOH) n wherein R is hydrogen, alkyl, alkenyl, alkynyl, acyl, alicyclic group, aryl, heteroaryl, or heterocyclic group, n is 1, 2, or 3, and is named by attaching peroxy before the parent acid. Preferably, R includes hydrogen, alkyl, or alkenyl. The terms "alkyl", "alkenyl", "alkynyl", "acyl", "alicyclic group", "aryl", "heteroaryl", and "heterocyclic group" are as defined herein.

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

[0061] As used herein, the terms "mixed" or "mixture", when used with respect to "percarboxylic acid composition", "percarboxylic acid", "peroxycarboxylic acid composition", or "peroxycarboxylic acid", refer to a composition or mixture containing 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 contain a peroxycarboxylic acid or peroxycarboxylic acid composition.

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

[0064] Next, the alkali source includes one or more bases or alkali compounds. Generally, an effective amount of the alkali source should be considered as the amount that provides a composition or a use solution of the composition having a pH of at least about 8. When the use solution has a pH of about 8 to about 10, it is considered weakly alkaline, and when the pH is greater than about 12, the solution can be considered caustic.

[0065] The alkali source can include an alkali metal carbonate, an alkali metal hydroxide, an alkali metal silicate, or a mixture thereof. Suitable metal carbonates that can be used include, for example, sodium or potassium carbonate, bicarbonate, sesquicarbonate, or a mixture thereof. Suitable alkali metal hydroxides that can be used include, for example, sodium hydroxide, lithium hydroxide, or potassium hydroxide. Examples of useful alkali metal silicates include sodium silicate or potassium silicate (having an M2O:SiO2 ratio of 2.4 to 5:1, where M represents an alkali metal) or metasilicate. The metasilicate can be prepared by mixing a hydroxide and a silicate. The alkali source can also include metal borates such as sodium borate or potassium borate.

[0066] The alkali source can also include ethanolamine, urea sulfate, amines, amine salts, and quaternary ammonium. Amine salts and quaternary ammonium compounds, which are the simplest cationic amines, are schematically depicted as follows: [Chemical formula] In the formula, R represents a long alkyl chain, and R', R'', and R''' can each be either a long alkyl chain, a smaller alkyl group or aryl group, or hydrogen, and X represents an anion.

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

[0068] Polyamine The polyamine can have the general formula of NH2-[R 10’ n -NH2, (RNH) n -RNH2, H2N-(RNH) n -RNH2, or H2N-(RN(R')) n -RNH2, but is not limited to these, where R 10’ is a straight-chain or branched-chain unsubstituted or substituted C2 to C 10 ​an alkylene group, or combinations thereof, where R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4~C 10 an alkylene group, or combinations thereof, where R’ is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4~C 10 an alkyl group, RNH2, RNHRNH2, or RN(RNH2)2, and n can be from 2 to 1,000,000. The monomers in the polyamine, for example, the R or R’ groups, may be the same or different. In the present disclosure, polyamine refers to both small molecule polyamines when n is from 1 to 9 and high molecular weight polyamines when n is from 10 to 1,000,000.

[0069] Examples of 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 JEFFAMINE® monoamines, diamines, and triamines by Huntsman. These highly multifunctional products typically contain primary amino groups bonded to the ends of a polyether backbone based on propylene oxide (PO), ethylene oxide (EO), or a mixture of both oxides. JEFFAMINE® amines include a family of polyetheramines consisting of monoamines, diamines, and triamines based on a core polyether backbone structure. JEFFAMINE® amines also include high conversion rate and polytetramethylene glycol (PTMEG)-based polyetheramines. These JEFFAMINE® amines have an average molecular weight (M w ) of about 130 to about 4,000.

[0071] The polyamines used in the present disclosure can be polyamine derivatives or modified polyamines, and one or more of the NH protons in the polyamine are substituted, although not all, by unsubstituted or substituted groups. For example, alkyl polyamines containing one or more alkyl groups attached to nitrogen atoms can be used to produce the multiply charged cationic or anionic compounds disclosed herein. In these PEI derivatives, only some of the primary NH2 or secondary NH protons are replaced by other non-proton groups, and the remaining NH2 or NH protons can still react with Michael acceptors such as activated olefins containing hydrophilic (ionic) groups by azo-Michael addition reactions.

[0072] One classification of polymeric polyamines includes polyethyleneimine (PEI) and its derivatives. Polyethyleneimine (PEI) or polyaziridine is a polymer having repeating units of CH2CH2NH, with a general formulation of NH2(CH2CH2NH) n -CH2CH2NH2, where n can be from 2 to 10 5 and can be. 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 containing primary, secondary, and tertiary amino groups. There also exist fully branched dendritic forms, containing primary and tertiary amino groups. Figures for unmodified linear, branched, and dendritic PEI are shown below.

Chemical formula

[0074] PEI derivatives are usually obtained by substituting 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. The ethoxylation of PEI can increase its solubility.

[0075] PEI is produced on an industrial scale. Various commercially available polyethyleneimines are available, for example, those sold under the trade names of 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 w ) of approximately 800, approximately 1,300, approximately 2,000, approximately 5,000, approximately 25,000, approximately 1,300 / 2,000 / 5,000, approximately 25,000, approximately 750,000, approximately 750,000, approximately 1,000,000, and approximately 2,000,000, respectively.

[0076] Two averages commonly used for the molecular weight of a polymer are the number average molecular weight (M n ) and the weight average molecular weight (M w ). The polydispersity index (D) represents the molecular weight distribution of the 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 the index number i represents the number of different molecular weights present in the sample, and n iis the sum of the number of moles and the molar mass of M i For polymers, M n and M w are usually different. For example, a PEI compound can have an M n of about 10,000 by GPC and an M w of about 25,000 by LS.

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

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

[0079] Suitable polyethyleneimines useful in the present disclosure can 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 can be any ratio, for example, in a ratio of about 1:1:1 to about 1:2:1 branching every 3 - 3.5 nitrogen atoms along the chain segment. Alternatively, a suitable polyethyleneimine compound can mainly be one of primary, secondary, or tertiary amine substituents.

[0080] The polyamines that can be used to prepare the multiply charged cationic or anionic compounds disclosed herein can have various average molecular weights thereof. Different multiply charged cationic or anionic compounds having their characteristic average molecular weights can be produced by selecting different starting small molecule polyamines, high molecular weight PEI, or mixtures thereof. By controlling the size of the polyamine or PEI and the degree of modification with an activated olefin containing an ionic group, multiply charged cationic or anionic compounds having a similar average molecular weight and a large number of cationic charges or a large number of anionic charges can be produced. Because of 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, the polyamines that can be used to prepare the multiply charged cationic or anionic compounds disclosed herein have an average molecular weight (M w ) 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 - 750,000, about 750,000 - 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.

[0082] The aza-Michael addition reaction between polyamine and activated olefin The multi-charged cationic or anionic compounds disclosed herein are derived from an aza-Michael addition reaction between a polyamine and an activated olefin containing a hydrophilic ionic group.

[0083] When an aliphatic amine group comes into contact with an unsaturated hydrocarbon moiety (e.g., a carbon-carbon double bond) near an electron-withdrawing group such as a carbonyl, cyano, or nitro group, an aza-Michael addition reaction can occur. Specifically, the Michael addition is a reaction between a nucleophile and an activated olefin and alkyne functionality, and the nucleophile adds across a carbon-carbon multiple bond 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, acrylate esters, alkyl methacrylates, acrylonitrile, acrylamide, maleimide, cyanoacrylate and vinyl sulfone, vinyl ketone, nitroethylene, α,β-unsaturated aldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridine, azo compounds, beta-ketoacetylene, and acetylene esters.

[0084] As used herein, "activated olefin" refers to a substituted alkene in which at least one of the double bond carbons has a conjugated electron-withdrawing group. Examples of activated olefins include, but are not limited to, α,β-unsaturated carbonyl compounds (CH2=CHCO-NH-CH3, alkyl-CH=CH-CO-alkyl, CH2=CH2C(O)-O-CH3), CH2=CH-COOH, CH2=CH(CH3)-COOH, CH2=CH-SO3H, etc.).

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

[0086] The aza-Michael addition reaction can be catalyzed by strong acids or strong bases. In some cases, some ionic liquids can function as both the reaction medium and the catalyst. A preferred catalyst for the aza-Michael addition reaction for synthesizing the disclosed compounds is a base. Exemplary base catalysts can be hydroxides and amines. Since the reaction for synthesizing the disclosed compounds uses a polyamine that usually contains a polyamine group, the primary polyamine group itself can function as a catalyst for the reaction. In such embodiments, no additional catalyst is necessary or the additional catalyst 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 unreactive to the solvent, various solvents can be used in the reaction. When a solvent (or diluent) is used, the filling level can range from about 10% by weight to a maximum of about 80% by weight or more. The solvent filling level can be about 0% by weight, about 1% to about 10% by weight, about 10% to about 20% by weight, about 20% to about 30% by weight, about 30% to about 40% by weight, about 40% to about 50% by weight, about 50% to about 60% by weight, about 60% to about 70% by weight, about 70% to about 80% by weight, about 1% to about 20% by weight, about 20% to about 40% by weight, about 40% to about 60% by weight, about 60% to about 80% by weight, about 40% to about 70% by weight, at least about 5% by weight, about 15% by weight, about 25% by weight, about 35% by weight, about 45% by weight, about 55% by weight, about 65% by weight, about 75% by weight, or any value in between in the final reaction mixture.

[0088] Generally, the reaction can be carried out at temperatures over a variety 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 and the activated olefin can be 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 ℃ ~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 in between. The reaction temperature can be substantially the same from the start to the end of the reaction, or can be changed from one temperature to another while the reaction is continuing.

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

[0090] The reaction for the synthesis of the compounds disclosed herein can be completed when 1 mole of polyamine and 2 moles or more of activated olefin are mixed together at the above temperature for a sufficient time.

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

[0092] Other inverse emulsion breaking composition agents in the inverse emulsion breaking composition In addition to the multiply charged cationic or anionic compounds derived from the polyamines described herein, the inverse emulsion breaking compositions in the present disclosure contain one or more additional inverse emulsion breaking composition agents.

[0093] Additional reverse emulsion breaking compositions in the disclosed reverse emulsion breaking compositions can include, but are not limited to, acids, carriers, dispersants, biocides, inorganic salts, organic salts, emulsifiers, additional reverse emulsion breakers, corrosion inhibitors, antioxidants, polymer degradation inhibitors, permeability modifiers, foaming agents, defoamers, fracturing proppants, glass microparticles, sand, fracturing proppant / sand control agents, scavengers for H2S, CO2, and / or O2, gelling agents, lubricants, and friction reducers, salts, or mixtures thereof.

[0094] Additional reverse emulsion breaking composition 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] Furthermore, the additional reverse emulsion breaking composition agents can be sequestering agents, solubilizers, lubricants, buffers, detergents, rinsing aids, preservatives, binders, thickeners or other viscosity modifiers, processing aids, carriers, water regulators, or foaming agents, threshold agents or systems, aesthetic improvers (e.g., dyes, odorants, fragrances), or other additives suitable for blending with reverse emulsion breakers, or mixtures thereof.

[0096] The additional reverse emulsion breaking compositions in the REB compositions will vary depending on the particular reverse emulsion breaking composition being manufactured and will be understood by those skilled in the art for its intended use.

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

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

[0099] Biocide and carrier In some embodiments, the inverse emulsion breaking compositions disclosed herein further comprise a biocide. In some embodiments, the inverse emulsion breaking compositions disclosed herein further comprise a carrier. In some embodiments, the inverse emulsion breaking compositions disclosed herein further comprise a biocide and a carrier. In some embodiments, the methods or inverse emulsion breaking compositions disclosed herein can consist of one or more of the multiply charged cationic or anionic compounds and carriers disclosed herein. In some embodiments, the inverse emulsion breaking compositions disclosed herein consist of one or more of the multiply charged cationic or anionic compounds, carriers, and biocides disclosed herein.

[0100] Biocides suitable for use can be oxidizing or non-oxidizing biocides. Examples of oxidizing biocides include, but are not limited to, bleaching agents, chlorine, bromine, chlorine dioxide, peroxycarboxylic acids, peroxycarboxylic acids, and materials capable of releasing chlorine, bromine, or peroxide. Examples of non-oxidizing biocides include, but are not limited to, glutaraldehyde, isothiazoline, 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(dimethylimino)ethylene(dimethylimino)ethylene dichloride, methylenebisthiocyanate, 2-decylthioethanamine, tetrakis(hydroxymethyl)phosphonium 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 (such as formaldehyde, glutaraldehyde, and acrolein), amine-type compounds (such as quaternary amine compounds and coco diamine), halogenated compounds (such as 2-bromo-2-nitropropane-1,3-diol (Bronopol) and 2,2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (such as isothiazolone, carbamate, and metronidazole), and quaternary phosphonium salts (such as tetrakis(hydroxymethyl)-phosphonium sulfate (THPS)).

[0102] Suitable oxidizing biocides include, for example, sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorinated hydantoin, stabilized sodium hypobromite, activated sodium bromide, brominated hydantoin, chlorine dioxide, ozone, peroxycarboxylic acid, peroxycarboxylic acid composition, and peroxide.

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

[0104] The carrier in the disclosed inverse emulsion breaking composition 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 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 a combination thereof, but are not limited thereto.

[0105] The composition can include one or more carriers in an amount of about 1 wt% to about 80 wt%, about 5 wt% to about 50 wt%, about 5 wt% to about 45 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 35 wt%, about 10 wt% to about 25 wt%, or about 10 wt% to about 35 wt% based on the total weight of the composition.

[0106] Corrosion inhibitor 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 can consist of one or more of the 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 of the multiply charged cationic or anionic compounds disclosed herein, a carrier, a corrosion inhibitor, and a biocide.

[0107] The reverse emulsion breaking composition can comprise from about 0.1 wt% to about 20 wt%, from about 0.1 wt% to about 10 wt%, or from 0.1 to about 5 wt% of one or more corrosion inhibitors, based on the total weight of the composition. The compositions of the present disclosure can comprise from about 0 wt% to about 10 wt% 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 can have its own requirements for the use of a corrosion inhibitor, and the weight percent of one or more corrosion inhibitors in the composition can vary depending on the production fluid in which it is used.

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

[0109] One or more corrosion inhibitors can be imidazoline compounds, quaternary ammonium compounds, pyridinium compounds, or combinations thereof.

[0110] One or more corrosion inhibitor components can be imidazoline. Imidazoline can be, for example, imidazoline derived from diamines such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), and long-chain fatty acids such as tall oil fatty acid (TOFA). Imidazoline can be imidazoline of formula (1A) or an imidazoline derivative. Representative imidazoline derivatives include imidazolinium compounds of formula (2A) or bis-quaternized compounds of formula (3A).

[0111] One or more corrosion inhibitors can include imidazoline of formula (1A),

Chemical formula

[0112] One or more additional corrosion inhibitors can be an imidazolinium compound of formula (2A),

Chemical formula

[0113] One or more additional corrosion inhibitors can be a bis-quaternized compound having formula (3A),

Chemical formula

[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] One or more corrosion inhibitors may be a bis-quaternized imidazoline compound having formula (3A), wherein R 1a and R 2a are each independently C6-C 22 alkyl, C8-C 20 alkyl, C 12 -C 18 alkyl, or C 16 -C 18 alkyl, or combinations thereof, and R 4a is C1-C 10 alkylene, C2-C8 alkylene, C2-C6 alkylene, or C2-C3 alkylene, x is 2, y is 1, n is 0, L1 is -COOH, -SO3H, or -PO3H, and L2 is absent or H. Preferably, the bis-quaternized compound has formula (3A), wherein R 1a and R 2a are each independently C 16 -C 18 alkyl, R 4a is -C2H2-, x is 2, y is 1, n is 0, L1 is -COOH, -SO3H, or -PO3H, and L2 is absent or H.

[0116] One or more additional corrosion inhibitors may be a quaternary ammonium compound of formula (4A), [Chemical formula] In the formula, R 1a , R 2a , and R 3a are independently C1-C 20 alkyl, R 4a is methyl or benzyl, and X - is a halide or 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 - , including alkylaryl, arylalkyl, and arylamine quaternary salts, where R 5a , R 6a , R 7a , and R 8a contain 1 to 18 carbon atoms and X is Cl, Br, or I. For the quaternary salts, R 5a , R 6a , R 7a , and R 8a can each independently be alkyl (e.g., C1-C 18 alkyl), hydroxyalkyl (e.g., C1-C 18 hydroxyalkyl), and arylalkyl (e.g., benzyl). Monocyclic or polycyclic aromatic amine salts with alkyl or alkylaryl halides are salts of the formula [N + R 5a R 6a R 7a R 8a [X - , where R 5a , R 6a , R 7a , and R 8a contain 1 to 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 (the above alkyl groups having 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] One or more corrosion inhibitors can be pyridinium salts such as those represented by formula (5A),

Chemical formula

[0120] One or more additional corrosion inhibitors can be phosphate esters, monomeric or oligomeric fatty acids, alkoxylated amines, or mixtures thereof.

[0121] One or more corrosion inhibitors can be phosphate esters. Suitable mono-, di-, and tri-alkyl, as well as mono-, di- and tri-ethanolamine alkylaryl phosphate esters, and phosphate esters typically contain from 1 to about 18 carbon atoms. Preferred mono-, di-, and tri-alkyl phosphate esters, alkylaryl, or arylalkyl phosphate esters are C3 - C 18 Those prepared by reacting aliphatic alcohols with phosphorus pentoxide. The phosphate ester intermediate exchanges its ester groups with triethyl phosphate to produce a wider distribution of alkyl phosphate esters.

[0122] Alternatively, phosphate esters can be made by admixing alkyl diesters with a mixture of low molecular weight alkyl alcohols or diols. The low molecular weight alkyl alcohols or diols preferably contain C6 - C 10 Alcohol or diol. Further, phosphate esters of polyols containing one or more 2-hydroxyethyl groups and their salts, and hydroxylamine phosphate esters obtained by reacting polyphosphoric acid or phosphorus pentoxide with hydroxylamines such as diethanolamine or triethanolamine are preferred.

[0123] One or more corrosion inhibitors can be monomeric or oligomeric fatty acids. Preferred monomeric or oligomeric fatty acids are C 14 -C 22 Saturated and unsaturated fatty acids, and dimer, trimer, and oligomer products obtained by polymerizing one or more of such fatty acids.

[0124] One or more corrosion inhibitors can be alkoxylated amines. The alkoxylated amines can be ethoxylated alkylamines. The alkoxylated amines can be ethoxylated tallow amines.

[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 a corrosion inhibitor. Since the disclosed multiply charged cationic or anionic compounds can be REB agents and corrosion inhibitors, the disclosed REB compositions have the advantage of using fewer chemicals for oil and gas operations.

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

[0127] The dispersant can be an acrylic acid polymer, a maleic acid polymer, a copolymer of acrylic acid and a sulfonated monomer, their alkyl esters, or combinations thereof. These polymers can include terpolymers of acrylic acid, acrylamide, and a sulfonated monomer. These polymers can also include quaternary polymers consisting of acrylic acid and three other monomers.

[0128] Suitable dispersants include aliphatic phosphonic acids having 2 to 50 carbons, such as hydroxyethyldiphosphonic acid, and aminoalkylphosphonic acids, such as polyaminomethylenephosphonates having 2 to 10 N atoms (for example, each having at least one methylenephosphonic acid group), but are not limited thereto. Examples of the latter include ethylenediaminetetra(methylenephosphonate), diethylenetriaminepenta(methylenephosphonate), and triamine- and tetraamine-polymethylenephosphonates, each having 2 to 4 methylene groups between each N atom and at least 2 of the number of methylene groups in each phosphonate being different. Other suitable dispersants include lignin, or derivatives of lignin such as lignosulfonates, and naphthalenesulfonic acid and derivatives.

[0129] The inverse emulsion breaking compositions disclosed herein can further comprise an organic sulfur compound such as 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 combinations thereof. Preferably, the mercaptoalkyl alcohol includes 2-mercaptoethanol. Such compounds are used as synergists in the composition. The organic sulfur compound can constitute from about 0.5 wt% to about 15 wt%, preferably from about 1 wt% to about 10 wt%, more preferably from about 1 wt% to about 5 wt% of the composition based on the total weight of the composition. The organic sulfur compound can constitute about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, or about 15 wt% of the composition.

[0130] The inverse emulsion breaking composition can further include an anti-emulsifier. Preferably, the anti-emulsifier includes an oxyalkylate polymer such as a polyalkylene glycol. The anti-emulsifier can constitute about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 4 wt% of the composition based on the total weight of the composition. The anti-emulsifier can constitute about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5 wt% of the composition.

[0131] The inverse emulsion breaking composition can further include an asphaltene inhibitor. The composition can include 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 the asphaltene inhibitor based on the total weight of the composition. Suitable asphaltene inhibitors include, but are not limited to, aliphatic sulfonic acids, alkylaryl sulfonic acids, aryl sulfonates, lignosulfonates, alkylphenol / aldehyde resins and similar sulfonated resins, polyolefin esters, polyolefinimides, polyolefin esters having alkyl, alkylene phenyl or alkylene pyridyl functional groups, polyolefin amides, polyolefin amides having alkyl, alkylene phenyl or alkylene pyridyl functional groups, polyolefinimides having alkyl, alkylene phenyl or alkylene pyridyl functional groups, alkenyl / vinyl pyrrolidone copolymers, graft polymers of polyolefins with maleic anhydride or vinyl imidazole, hyperbranched polyester amides, polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkyl succinates, sorbitan monooleate, and polyisobutylene succinic anhydride.

[0132] The inverse emulsion breaking composition can further contain a paraffin inhibitor. The composition can contain 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 paraffin inhibitor based on the total weight of the composition. Suitable paraffin inhibitors include, but are not limited to, paraffin crystal modifiers and combinations of dispersants / crystal modifiers. Suitable paraffin crystal modifiers include, but are not limited to, alkyl acrylate copolymers, alkyl acrylate vinyl pyridine copolymers, ethylene vinyl acetate copolymers, maleic anhydride ester copolymers, branched polyethylene, naphthalene, anthracene, microcrystalline wax, and / or asphaltenes. Suitable paraffin dispersants include, but are not limited to, dodecylbenzene sulfonate, oxyalkylated alkylphenol, and oxyalkylated alkylphenol resin.

[0133] The inverse emulsion breaking composition can further contain a scale inhibitor. The composition can contain from about 0.1 wt% to about 20 wt%, from about 0.5 wt% to about 10 wt%, or from about 1 wt% to about 5 wt% 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 acid, phosphonates, phosphonic acid, polyacrylamide, salts of acrylamide methyl propane sulfonate / acrylic acid copolymer (AMPS / AA), phosphorylated maleic acid copolymer (PHOS / MA), mono-, bis-, and oligomer phosphinopoly succinic acid (PSO) derivatives, polycarboxylic acids, hydrophobically modified polycarboxylic acids, and salts of polymaleic acid / acrylic acid / acrylamide methyl propane sulfonate terpolymer (PMA / AA / AMPS).

[0134] The inverse emulsion breaking composition can further contain an emulsifier. The composition can contain about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 4 wt% of the 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 can further contain a water clarifier. The composition can contain about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 4 wt% 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 can further contain an emulsion breaker. The composition can contain about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 4 wt% of the emulsion breaker based on the total weight of the composition. Suitable emulsion breakers include, but are not limited to, dodecylbenzenesulfonic acid (DDBSA), sodium salt of xylene sulfonic acid (NAXSA), epoxidized and propoxylated compounds, anionic, cationic, and nonionic surfactants, and resins such as phenols and epoxy resins.

[0137] In some embodiments, the emulsion breaker is a nonionic emulsion breaker. Suitable nonionic emulsion breakers include polyethers or oxyalkylates derived from diols, triols, and polyols; polyesters derived from polyethers and diacids or polyacids such as adipic acid, fumaric acid, maleic anhydride, or acrylic acid; para-substituted alkylphenol resin oxyalkylates derived from t-butylphenol, t-amylphenol, nonylphenol, or butylnonylphenol; polymerized polyethers derived from toluene di-isocyanate, diglycidyl ether of bisphenol-A, or acrylic acid; and combinations of resin oxyalkylates with polymerized polyols such as maleic acid copolymerized with acrylic acid and then further esterified, but are not limited thereto.

[0138] The reverse emulsion breaking composition can further include a hydrogen sulfide scavenger. The composition can include from about 1 wt% to about 50 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 0.1 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, or from about 0.5 wt% to about 4 wt% of a hydrogen sulfide scavenger, based on the total weight of the composition. Suitable additional hydrogen sulfide scavengers include oxidizing agents (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 and aldehydes, and condensation products of alkyl alcohols and aldehydes, but are not limited thereto.

[0139] The inverse emulsion breaking composition can further contain a gas hydrate inhibitor. The composition can contain from about 0.1 wt% to about 25 wt%, from about 0.5 wt% to about 20 wt%, from about 1 wt% to about 10 wt%, from about 0.1 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, or from about 0.5 wt% to about 4 wt% 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 (THIs), kinetic hydrate inhibitors (KHIs), and anti-aggregation agents (AAs). Suitable thermodynamic hydrate inhibitors include 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)), 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), but are not limited thereto.

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

[0141] The inverse emulsion breaking composition can further include a pH adjuster. The composition can include from about 0.1 wt% to about 20 wt%, from about 0.5 wt% to about 10 wt%, or from about 0.5 wt% to about 5 wt% 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 can further contain a surfactant. The composition can contain from about 0.1 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, or from about 0.5 wt% to about 4 wt% of the surfactant based on the total weight of the composition. Suitable surfactants include, but are not limited to, anionic surfactants and nonionic surfactants. Examples of 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 phosphates, and mono and dialkyl sulfosuccinates and sulfosuccinates. Examples of nonionic surfactants include alcohol alkoxylates, alkylphenol alkoxylates, block copolymers of ethylene, propylene, and butylene oxides, alkyl dimethyl amine oxides, alkyl bis(2-hydroxyethyl) amine oxides, alkylamidopropyl dimethyl amine oxides, alkylamidopropyl bis(2-hydroxyethyl) amine oxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitan esters, and polyalkoxylated sorbitan esters, and acyl polyethylene glycol esters and diesters. Betaines and sultanes, zwitterionic surfactants such as alkyl amphoacetates and amphodiacetates, alkyl amphopropionates and amphodipropionates, and alkyliminodipropionates are also included.

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

[0144] Alternatively, the inverse emulsion breaking composition contains no additional agents or additives.

[0145] Additionally, the inverse emulsion breaking composition can be formulated with a composition containing the following components, as shown in Table 1. These formulations include the ranges of the listed components and can optionally include additional agents. The values in the following table are in weight percent.

Table 1

Table 2

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

[0147] The inverse emulsion breaking composition or the multiply charged cationic or anionic compound can be used to break inverse emulsions 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 an inverse emulsion breaking composition or a multiply charged cationic or anionic compound can be introduced can be a liquid containing hydrocarbons. The liquid hydrocarbon can be any type of liquid hydrocarbon including, but not limited to, crude oil, heavy oil, processed residue oil, asphalt oil, coker oil, coker light oil, fluid catalytic cracking feedstock, light 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 an inverse emulsion breaking composition or a multiply charged cationic or anionic compound can be at any selected temperature such as ambient temperature or elevated temperature. The fluid (e.g., liquid hydrocarbon) or gas can be at a temperature of about 40°C to about 250°C. The fluid or gas can 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 can 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 the multiply charged cationic or anionic compound 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 total dissolved solids (TDS) of 0% to 25%, about 1% to 24%, or about 10% to 25% weight / weight (w / w).

[0152] Inverted emulsion breaking compositions or production fluids or gases into which multiply charged cationic or anionic compounds are 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 an oil wellhead. The equipment can be a cargo ship, a storage ship, a storage tank, or a pipeline connecting a ship or a processing unit.

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

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

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

[0156] Inverted emulsion breaking compositions or multiply charged cationic or anionic compounds can be introduced into liquids as well as mixtures of several liquids, liquids and gases, liquids, solids, and gases. The inverted emulsion breaking compositions or 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 can pass through an absorption tower containing an inverted emulsion breaking composition or a multiply charged cationic or anionic compound.

[0158] An inverted emulsion breaking composition or a multiply charged cationic or anionic compound can be applied to the production fluid or gas to provide any selected concentration. In practice, the inverted emulsion breaking composition or the multiply charged cationic or anionic compound is typically added to the flow line to provide an effective treatment input amount of about 0.01 to about 5,000 ppm of the inverted emulsion breaking composition or the multiply charged cationic or anionic compound. An inverted emulsion breaking composition or a multiply charged cationic or anionic compound can be applied to the production fluid or gas to provide an active concentration of about 1 part per million (ppm) to about 1,000,000 ppm, about 1 part per million (ppm) to about 100,000 ppm, or about 10 ppm to about 75,000 ppm. Applying a multiply charged cationic or anionic compound or their salts / compositions to the fluid can 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. The active concentration means the concentration of the inverted emulsion breaking composition or the multiply charged cationic or anionic compound.

[0159] Inverted emulsion breaking compositions or multiply charged cationic or anionic compounds can be applied to a production fluid or gas to provide an active concentration in the treated production fluid 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. Inverted emulsion breaking compositions or multiply charged cationic or anionic compounds can be applied to a production fluid to provide an active concentration in the treated production fluid 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. Each production fluid can have its own dosage level requirements, and the effective dosage levels of the inverted emulsion breaking composition or multiply charged cationic and anionic compounds to sufficiently break an inverted emulsion or multiple emulsion can vary depending on the production fluid in which it is used.

[0160] Inverted emulsion breaking compositions or multiply charged cationic or anionic compounds can be applied continuously, in batches, or in combinations thereof. Administration of the inverted emulsion breaking composition or multiply charged cationic or anionic compounds can be continuous. Administration of the inverted emulsion breaking composition or multiply charged cationic or anionic compounds can be intermittent (e.g., batch processing), or continuous / maintenance and / or intermittent.

[0161] Feed rates for continuous processing are typically in the range of about 10 to about 500 ppm, or about 10 ppm to about 200 ppm. Feed rates for continuous processing are typically in the range of about 10 ppm to about 400,000 ppm, or about 10 ppm to about 20,000 ppm. Inverted emulsion breaking compositions or multiply charged cationic or anionic compounds can be applied as tablets to a pipeline to provide compositions at high feed rates (e.g., 20,000 ppm).

[0162] The flow rate of the inverse emulsion breaking composition or the multi-charged cationic or anionic compound used in the flow line can be from 0.1 to 100 feet per second, or from 0.1 to 50 feet per second. The inverse emulsion breaking composition or the multi-charged cationic or anionic compound can also be formulated with water to facilitate addition to the flow line.

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

[0164] The inverse emulsion breaking composition or the multi-charged cationic or anionic compound can be dispensed by intermittently or continuously immersing it in water or the production fluid. The inverse emulsion breaking composition or the multi-charged cationic or anionic compound can then dissolve, for example, at a controlled rate or a predetermined rate. This rate can be effective to maintain the concentration of the dissolved compound or composition that is effective for use according to the methods disclosed herein.

[0165] The reverse emulsion breaker compositions disclosed herein can comprise from about 10 wt% to about 90 wt% carrier, biocide, corrosion inhibitor, additional REB agent, combinations thereof, and from about 10 wt% to about 90 wt% of one or more multiply charged cationic or anionic compounds, from about 20 wt% to about 80 wt% carrier, biocide, corrosion inhibitor, additional REB agent, or combinations thereof, and from about 20 wt% to about 80 wt% of one or more multiply charged cationic or anionic compounds, from about 30 wt% to about 70 wt% carrier, biocide, corrosion inhibitor, additional REB agent, or combinations thereof, and from about 30 wt% to about 70 wt% of one or more multiply charged cationic or anionic compounds, or from about 40 wt% to about 60 wt% carrier, biocide, corrosion inhibitor, additional REB agent, combinations thereof, and from about 40 to about 60 wt% of one or more multiply charged cationic or anionic compounds.

[0166] Additionally, when using a reverse emulsion breaker to break an emulsion in a production fluid in an oil and gas operation, an optional emulsion breaker and the reverse emulsion breaker composition can be added to the production fluid.

[0167] The emulsion breaker can comprise an oxyalkylated phenol-formaldehyde resin, a resin ester, an oxyalkylated polyalkylamine, a polyol, a crosslinked polyol having a difunctional or polyfunctional crosslinking agent, an isocyanate, an acid, or combinations thereof.

[0168] The reverse emulsion breaker composition can comprise a mixture of a 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 reverse emulsion breaker have a synergistic effect for breaking water-in-oil-in-water emulsions in the production fluid of an oil production system. The emulsion breaker can have a concentration in the production fluid from about 100 ppm to about 400 ppm.

[0170] The 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 for the REB compositions disclosed herein or suitable 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 usually used in production fluids with a high bitumen content (e.g., 70 wt%). SCO has a typical density of 650 - 750 kg / m3 and is used in production fluids with a low bitumen content (e.g., 50 wt%).

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

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

[0174] The inverse emulsion breaking composition disclosed herein is preferably added to the incoming emulsion to a water and oil separation system. The emulsion breaker, inverse emulsion breaker, or combinations thereof can be added at an injection point in the incoming pipeline of the production fluid before placing the production fluid in 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. Further, the diluent can be injected at different injection points. The separation vessel can be a free water knockout (FWKO) vessel, a heat treatment unit, or a phase separator.

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

[0176] In one aspect, herein is a compound derived from an aza-Michael addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) having an ionic group according to one of the following formulas,

Chemical formula

[0177] In some embodiments, the polyamine is NH2-[R 10’ n -NH2, (RNH) n -RNH2, H2N-(RNH) n -RNH2, or H2N-(RN(R’)) n -RNH2, where R 10’ is a straight-chain or branched-chain unsubstituted or substituted C2 to C 10 alkylene group, or a combination thereof, R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a straight-chain or branched-chain unsubstituted or substituted C4 to C 10 alkylene group, or a combination thereof, R’ is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a straight-chain or branched-chain unsubstituted or substituted C4 to C 10 alkyl group, RNH2, RNHRNH2, or RN(RNH2)2, and n can be from 2 to 1,000,000.

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

[0179] In FIGS. 1 and 2, k, l, m, n, o, or p is an integer from 1 to 100, X is NH or O, R 2 is H, CH3, or an unsubstituted straight-chain or branched-chain C2 to C 10 alkyl group, R 3 is absent or an unsubstituted straight-chain or branched-chain C1 to C 30 alkylene group, and Y is -NR​4 R 5 R 6(+) 、 or a salt thereof, where R 4 、R 5 、 and R 6 are independently a C1-C 10 alkyl group or a benzyl group.

[0180] The structures I and II in FIGS. 1 and 2 are generalized and illustrative depictions of reaction products. In structures I and II, since all secondary and primary amines of polyethyleneimine react with the activated olefin, no secondary amines remain. In the disclosed multiply charged cationic or anionic compounds, some secondary or primary amine groups do not react completely with the activated olefin and may remain as primary or secondary amine groups in or as salts of the multiply charged cationic or anionic compounds.

[0181] In other words, in some embodiments, the multiply charged cationic or anionic compound is NA2-[R 10’ n -NA2, (RNA) n -RNA2, A2N-(RNA) n -RNA2, or A2N-(RN(R’)) n -RNA2 and has one of the general formulas, where R 10’ is a straight-chain or branched-chain unsubstituted or substituted C2-C 10 alkylene group, or a combination thereof, R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a straight-chain or branched-chain unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, R’ is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a straight-chain or branched-chain unsubstituted or substituted C4-C 10 alkyl group, RNA2, RNARNA2, or RN(RNA2)2, n can be from 2 to 1,000,000, and A is H or [Chemical formula] ​ or one of combinations thereof, each compound containing at least two non-proton and cationic or anionic A groups, at least three non-proton and cationic or anionic A groups, at least four non-proton and cationic or anionic A groups, at least five non-proton and cationic or anionic A groups, or six or more cationic or anionic A groups. In some embodiments, A is H or positively charged [Chemical formula] is. In some other embodiments, A is H or negatively charged [Chemical formula] is.

[0182] In some embodiments, at least two of the primary NH2 protons are [Chemical formula] is, and the remainder of the primary NH2 protons remains. In some embodiments, at least two of the primary NH2 protons are [Chemical formula] is, and the remainder of the primary NH2 protons remains. In some other embodiments, all of the primary NH2 protons are [Chemical formula] is replaced by. In some embodiments, some of the primary NH2 and secondary NH protons are [Chemical formula] is replaced by. In some embodiments, some of all of the primary NH2 and secondary NH protons are [Chemical formula] 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 CH3. In still some other embodiments, R 2 is CH3CH3, CH2CH2CH3, or CH(CH3)2.

[0185] In some embodiments, Y is -NR4R5R6 (+) . In some other embodiments, Y is -NR4R5R6 (+) and R 4 , R 5 , and R 6 are independently CH3. In still some other embodiments, Y is -NR4R5R6 (+) and R 4 and R 5 are independently CH3 and R 6 is C2 - C 12 aromatic alkyl. In some other embodiments, Y is -NR4R5R6 (+) and R 4 and R 5 are independently CH3 and R 6 is -CH2 - C6H6.

[0186] In some embodiments, Y is -NR4R5R6 (+) 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 -SO3H, -OSO3H, or a salt thereof. In still some other embodiments, Y’ is -OPO3H, -PO3H, or a salt thereof. In some other embodiments, Y’ is an acid species or a salt thereof.

[0188] In some embodiments, R 3 is CH2. In some other embodiments, R 3 is CH2CH2. In other embodiments, R 3 is C(CH3)2. In still some other embodiments, R 3 is an unsubstituted, straight-chain, and saturated C1-C 10 alkylene group. In some embodiments, R 3 is an unsubstituted, straight-chain, and unsaturated C1-C 10 alkylene group.

[0189] In some embodiments, R 3 is a straight-chain C8-C 18 alkyl, alkenyl, or alkynyl group. In some other embodiments, R 3 is a branched-chain C8-C 20 alkyl, alkenyl, or alkynyl group.

[0190] In some embodiments, the polyamine is a straight-chain, branched-chain, or dendritic polyamine having the general formula of -[RNH] n -, wherein R is -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a straight-chain or branched-chain unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, and n is an integer of 3, 4, 5, 6, 7-9, or 10-1,000,000.

[0191] In some embodiments, the polyamine is (RNH) nA linear, branched, or dendritic polyamine having the general formula -RNH2, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, and 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 H2N-(RNH) n A linear, branched, or dendritic polyamine having the general formula -RNH2, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, linear or branched, unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, and 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 still some other embodiments, the polyamine is H2N-(RN(R’)) n A linear, branched, or dendritic polyamine having the general formula -RNH2, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, linear or branched unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, and R’ is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, linear or branched unsubstituted or substituted C4-C 10 alkyl group, RNH2, RNHRNH2, or RN(RNH2)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 NH2-[R 10’ n -NH2 having the general formula, where R 10’ is a linear or branched unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, and n is an integer from 3, 4, 5, 6, 7-9, or 10-1,000,000. In some other embodiments, R 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 includes an alkyleneamine, and the alkyleneamine includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, tris(2-aminoethyl)amine, or a mixture thereof.

[0197] In some other embodiments, the polyamine has a polyether backbone or is a mixture of monoamines, diamines, and triamines having 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 substituted by a non-proton group such as an alkyl.

[0199] ​In some further embodiments, the polyamine is an ethoxylated polyamine, a propylated polyamine, a polyamine having a polyquat, a polyamine having a polyglycerol, or a combination thereof.

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

[0201] In some other further 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. In some other embodiments, the polyamine is a mixture of two or more different polyamines, and the different polyamines have different molecular weights, different structures, or both.

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

[0204] In some embodiments, the polyamine has an average molecular weight (M w ) of about 60 to 200, about 100 to 400, about 100 to 600, about 600 to 5,000, about 600 to 800, about 800 to 2,000, about 800 to 5,000, about 100 to 2,000,000, about 100 to 25,000, about 600 to 25,000, about 800 to 25,000, about 600 to 750,000, about 800 to 750,000, about 25,000 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.

[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), or 2-(methacryloyloxy)-N,N,N-trimethylethane-1-aminium methyl sulfate (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-trimethylethane-1-aminium methyl sulfate (DMAEA-MSQ), or a mixture thereof.

[0210] In some embodiments, the activated olefin is acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinylsulfonic acid, vinylphosphonic acid, or a mixture 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 vinylsulfonic acid, vinylphosphonic acid, or a mixture thereof.

[0213] In still some other embodiments, when the activating olefin contains an anionic group capable of being negatively charged at alkaline pH, the counter cation for the negative charge includes, but is not limited to, alkali metal ions, Li + , Na + , K + , NH4 + , quaternary ammonium ions, and the like.

[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 compound is an aza-Michael addition reaction product of (3-acrylamidopropyl)trimethylammonium chloride (APTAC) with polyethyleneimine having an average molecular weight (M w ) of about 1,300, polyethyleneimine having an average molecular weight (M w ) of about 5,000, polyethyleneimine having an average molecular weight (M w ) of about 25,000, or polyethyleneimine having an average molecular weight (M w ) of about 750,000, respectively.

[0216] In some embodiments, the compound is [Chemical formula] one or more of the following, where n = 0 to 1000. When n is greater than 2, the compound can be a mixture of three or more cationic compounds, and it should be understood that the exact positions of NH substitution are different from each other.

[0217] In some other embodiments, the compound is [Chemical formula] as follows.

[0218] In some other embodiments, the compound is [Chemical formula] as follows.

[0219] In some other embodiments, the compound is [Chemical formula] as follows.

[0220] In some embodiments, the multiply charged cationic or anionic compound has an average molecular weight (M w ) of about 100 to about 2,000,000 Da. In some other embodiments, the multiply charged cationic or anionic compound has an average molecular weight (M w ) of about 100 to about 50,000 Da. In still some other embodiments, the multiply charged cationic or anionic compound has an average molecular weight (M w ) 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.

[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 10 to 1000 positive charges, or any value between the positive charges.

[0222] 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 negative charges. In some other embodiments, the compound has from 10 to 1000 positive charges, or any value between the negative charges.

[0223] In some embodiments, the compound is water-soluble or water-dispersible.

[0224] Production method In another aspect, provided herein is a method for preparing a compound or a salt thereof, the method comprising contacting a polyamine with an activated olefin (Michael acceptor) having an ionic group according to one of the following formulas:

Chemical formula

[0225] In some embodiments of the disclosed method, the polyamine is NH2-[R 10’ n -NH2, (RNH) n -RNH2, H2N-(RNH) n -RNH2, H2N-(RN(R’)) n -RNH2, or a mixture thereof, wherein R 10’ is a straight-chain or branched-chain unsubstituted or substituted C2-C 10 alkylene group, or a combination thereof, R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a straight-chain or branched-chain unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, R’ is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a straight-chain or branched-chain unsubstituted or substituted C4-C 10 alkyl group, RNH2, RNHRNH2, or RN(RNH2)2, and n can be from 2 to 1,000,000.

[0226] In other embodiments, the activated olefin is

Chemical formula

[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-trimethylethane-1-aminium methyl sulfate (DMAEA-MSQ), or a mixture thereof.

[0228] In some embodiments, Y is -NR4R5R6 (+) 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, hydrogen carbonate, hydrogen oxalate, hydrogen sulfate, hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

[0229] In some embodiments of the disclosed method, the activated olefin is [Chemical formula] wherein X is NH or O, and R 2 is H, CH3, or an unsubstituted straight or branched C2 to C 10 alkyl, alkenyl, or alkynyl group, R 2’ is H, CH3, or an unsubstituted or substituted straight or branched C1 to C 10 alkyl, alkenyl, alkynyl group, -COOH, -CH2COOH, Y', or -(CH2) m -Y', and m is an integer from 2 to 4, R 3is absent or is an unsubstituted linear or branched C1-C 30 alkylene group, Y’ is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H, or a salt thereof, and R 4 , R 5 , R 6 is independently a C1-C 10 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 a mixture 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 still some other embodiments, when the activated olefin contains an anionic group capable of being negatively charged at alkaline pH, examples of the counter cation for the negative charge include, but are not limited to, alkali metal ions, Li + , Na + , K + , NH4 + , quaternary ammonium ions, and the like.

[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 group 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, or after, one or both of the reactants, or before one or both of 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, a base, or an acid. The catalyst, base, or acid can be introduced into the reaction between the polyamine and the activated olefin by any method known to those skilled in the art.

[0236] In some embodiments, the contacting step is carried out in the absence of an additional base or alkali source. In some other embodiments, the contacting step is carried out in the presence of an alkali source. In some other embodiments, the contacting step is carried out in the presence of an organic base such as an alkanolamine. In still some other embodiments, the contacting step is carried out in the presence of an alkali metal hydroxide, carbonate, imidazole / pyridine base, or a combination thereof, for example, NaOH, Na2CO3, 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 reacting under solvent-free conditions at room temperature.

[0237] In still 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 Michael addition reactions.

[0238] In some further other embodiments of the disclosed method, the contacting step is carried out without including a catalyst, a base, or an acid. In some other embodiments, the contacting step is carried out without including an alkali metal hydroxide, a carbonate, a silicate, a metasilicate, an imidazole / pyridine-based base, or all of them. In some embodiments, the contacting step is carried out without including a base.

[0239] In yet another aspect, an article, product, or composition comprising one or more compounds disclosed herein or produced by the methods disclosed herein is disclosed herein.

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

[0241] As used herein, "stable" means that the compound disclosed herein does not precipitate or separate from the carrier solvent or any other component in the composition after the compound disclosed herein and the carrier solvent or any other component are homogeneously mixed 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.

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

[0245] In one aspect, disclosed herein is a composition for decomposing an inverse emulsion in a production fluid from an oil and gas production system, the inverse emulsion breaking composition comprising one or more of the compounds disclosed herein or salts thereof and one or more inverse emulsion breaking composition agents. In some embodiments, the inverse emulsion composition breaks a water-in-oil emulsion in the production fluid.

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

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

[0248] In some embodiments, the production fluid includes fresh water, recycled water, salt water, surface water, associated water, or mixtures thereof. In some embodiments, the production fluid is 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. In some other embodiments, the production fluid is associated water, which is the water portion of the production fluid after oil and contaminants have been removed.

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

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

[0252] In some embodiments, the reverse emulsion breaking composition includes a carrier, which is water, an organic solvent, or a mixture thereof.

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

[0254] In some embodiments, the organic solvent is alcohol, hydrocarbon, ketone, ether, alkylene glycol, glycol ether, amide, nitrile, sulfoxide, ester, or any combination thereof. In some other embodiments, the organic solvent is alcohol, alkylene glycol, alkylene glycol alkyl ether, or a combination thereof. In still some other 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, a mixture thereof with water, or any combination thereof.

[0256] In some embodiments, the reverse emulsion breaking composition further comprises one or more of corrosion inhibitors. In some embodiments, the reverse emulsion breaking composition further comprises one or more of corrosion inhibitors 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 contain 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, ClO2, bromine, ozone, hydrogen peroxide, peracetic acid, peroxymonosulfate, glutaraldehyde, dibromonitrilopropionamide, isothiazolone, terbuthylazine, polymeric biguanide, methylene bisthiocyanate, tetrakishydroxymethylphosphonium sulfate, and any combination thereof.

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

[0261] In some embodiments, the reverse emulsion breaking composition further comprises an organic sulfur compound. In some other embodiments, the organic sulfur compound is 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 wt% to about 20 wt%, from about 1 wt% to about 15 wt%, from about 1 wt% to about 10 wt%, from about 1 wt% to about 5 wt% 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 oxidizing agent, an inorganic peroxide, sodium peroxide, chlorine dioxide; C1-C 10 aldehyde, formaldehyde, glyoxal, glutaraldehyde, acrolein or methacrolein, triazine, monoethanolamine triazine, monomethylamine triazine, or a mixture thereof.

[0265] In some embodiments, the inverse emulsion breaking composition further comprises a surfactant. In some embodiments, the inverse 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 a mixture 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 inverse emulsion breaking composition further comprises a coagulant / flocculant, a water purifying agent, or a mixture thereof. In some embodiments, the inverse emulsion breaking composition further comprises an additional inverse emulsion breaker, a carrier, a corrosion inhibitor, a coagulant / flocculant, a water purifying agent, 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, an emulsion breaker, or a mixture thereof.

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

[0273] In some embodiments, the additional reverse emulsion breaker is an acrylic acid-based polymer, an acrylamide-based polymer, a polymerized amine, an alkanolamine, an organic polymer such as thiocarbamate, and an acryamidediallyldimethylammonium chloride (DADMAC) polymer and / or a methylacrylamide[3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) polymer, a copolymer of epichlorohydrin and dimethylamine or trimethylamine, a copolymer of acrylamide and dimethylaminoethyl acrylate (quaternized with methyl chloride, aluminum chlorohydrate (ACH) and polyaluminum chloride (PAC), acrylamide), a cationic polymer such as a DMAEA.MCQ copolymer.

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

[0275] In some embodiments, the reverse emulsion breaking composition further comprises an antioxidant, a polymer degradation inhibitor, a permeability regulator, a foaming agent, an antifoaming agent, an emulsifier, a scavenger for CO2 and / or O2, a gelling agent, a lubricant, a friction reducer, a salt, an alkali source, or a mixture thereof.

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

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

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

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

[0280] Use of the disclosed methods or compositions In some embodiments, for the methods disclosed herein, providing the REB composition in the production fluid means that the REB composition or the multiply charged cationic or anionic compound, or a solution thereof for use, is added into the production fluid. In some other embodiments, providing the REB composition in the production fluid means contacting the production fluid or adding the REB composition or the multiply charged cationic or anionic compound to the fluid used to make the production fluid. The REB composition or the multiply charged cationic or anionic compound, or a solution thereof for use, can be added continuously or intermittently when more compounds or compositions may be required.

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

[0282] In some embodiments, the reverse emulsion breaking composition is provided to an 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 then the use solution is provided into a production fluid. In some embodiments, the water for diluting the REB composition includes fresh water, recycled water, salt water, surface water, associated water, or mixtures thereof. In some embodiments, the water for diluting the REB composition is the production fluid.

[0284] Typically, the REB composition or its use solution is injected into the production fluid. In this scenario, 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 clarifier is

Chemical formula

[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, flocculant, coagulant, or water purifying agent is an oxyalkylated phenol-formaldehyde resin, resin ester, oxyalkylated polyalkylamine, polyol, crosslinked polyol having a difunctional or polyfunctional crosslinking agent, isocyanate, acid, or a combination thereof.

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

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

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

[0291] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water purifying agent is trithiocarbamic acid, dithiocarbamate, dimethylaminoethyl acrylate methyl chloride, benzyl chloride quaternary salt, polymeric quaternary ammonium betaine, metal salt, zinc chloride, aluminum chloride, polymeric quaternary ammonium salt, a copolymer of acrylic acid and acrylamide, or a mixture thereof.

[0292] In some embodiments, the emulsion breaker, REB, flocculant, coagulant, or water purifying 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 ) of 100,000 to 2,000,000 Da. 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 purifying agent is a low molecular weight polymeric cationic coagulant / flocculant, and the low molecular weight polymeric cationic coagulant / flocculant has an average molecular weight (M w ) of 10,000 to 100,000 Da. In some embodiments, the low molecular weight polymeric cationic coagulant / flocculant has 3 to 10 net charges.

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

[0295] In some embodiments, the high molecular weight polymeric anionic coagulant / flocculant has an average net charge of 10 to 1,000. In some other embodiments, the low molecular weight polymeric anionic coagulant / flocculant has 3 to 10 net charges.

[0296] In some embodiments, the emulsion breaker, REB, flocculant, flocculant, or water purifying agent is a high molecular weight polymeric coagulant / flocculant, and the high molecular weight polymeric non-ionic 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, the reverse emulsion breaking composition comprises one or more multi-charged cationic or anionic compounds, one or more emulsion breakers, and one or more diluents.

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

[0300] In some embodiments, the REB composition or multi-charged cationic or anionic compound disclosed herein, after administering the multi-charged cationic or anionic compound or mixture thereof, or the REB composition, 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, can break the water-in-oil emulsion in the production fluid as shown by a conventional bottle test as described in the Examples section of the present disclosure.

[0301] As used herein, the terms "substantially free of" or "free of" refer to a composition that either completely lacks the component or has a minor amount of the component that does not affect the performance of the composition. The component may be present as an impurity or a contaminant and must be less than about 0.5 weight percent. In another embodiment, the amount of the component is less than about 0.1 weight percent, and in yet another embodiment, the amount of the component is less than about 0.01 weight percent.

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

[0303] The methods and compositions of the present disclosure can include, consist essentially of, or consist of the components and ingredients of the disclosed compositions or methods, as well as other ingredients described herein. As used herein, "consisting essentially of" means that a method and composition 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 recited in the claims.

Examples

[0304] Embodiments of the present disclosure are further defined in the following non-limiting examples. These examples illustrate certain specific embodiments of the present disclosure but are provided merely by way of illustration. From the above considerations and these examples, those skilled in the art can identify the essential features of the present disclosure and make various changes and modifications to the embodiments of the present disclosure to adapt it to various usage methods and conditions without departing from its spirit and scope. Accordingly, various modifications to 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 be within the scope of the appended claims.

[0305] Example 1 Synthesis of Multiply Charged Cationic Compound 1 (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 96 grams) and water (20 grams) were charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, temperature probe, and condenser. Then, tetraethylenepentamine (TEPA, 12 grams) was 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 this reaction was monitored for monomer consumption by ESI-MS and / or NMR spectroscopy. The aqueous solution of the obtained Compound 1 was used as such for its application test as REB.

[0306] Example 2 Synthesis of Multiply Charged Cationic Compound 2 For this reaction, ethyleneamine E-100 from Huntsman was used. E-100 is a mixture of tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexaethyleneheptamine (HEHA), and other high molecular weight amines. E-100 is a complex mixture of various linear, cyclic, and branched amines having a number average molecular weight (M n ) of 250 - 300 g / mol.

[0307] (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 60 grams) and water (20 grams) were charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, ethyleneamine E-100 (12 grams) was 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%. For the application test, the obtained aqueous solution of Compound 2 was used as it was.

[0308] Example 3 Synthesis of Multiply Charged Cationic Compound 3 (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 70 grams) and water (20 grams) were charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, pentaethylenehexamine (PEHA, 10 grams, 99%) was 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%. For the application test, the obtained aqueous solution of Compound 3 was used as it was.

[0309] Example 4 Synthesis of Multiply Charged Cationic Compound 4 (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 130 grams) and water (20 grams) were charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, diethylenetriamine (DETA, 10 grams) was 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 reaction temperature was raised to 80 °C and stirred overnight or until the consumption of APTAC exceeded 98%. For the application test, the obtained aqueous solution of Compound 4 was used as it was.

[0310] Example 5 Synthesis of Multiply Charged Cationic Compound 5 BASF Lupasol G20 (weight average molecular weight (Mw )(An aqueous solution of polyethyleneimine having an approximate molecular weight of 1,300 g / mol) was used in this reaction.

[0311] (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 78.55 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Next, Lupasol G20 (50%, 50 grams) was 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%. For the application test, the aqueous solution of the obtained compound 5 was used as it was.

[0312] Example 6 Synthesis of Multiply Charged Cationic Compound 6 BASF Lupasol G100 (weight average molecular weight (M w )(An aqueous solution of polyethyleneimine having an approximate molecular weight of 5,000 g / mol) was used in this reaction.

[0313] (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 72.4 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Next, Lupasol G100 (50%, 50 grams) was 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%. For the application test, the aqueous solution of the obtained compound 6 was used as it was.

[0314] Example 7 Effect of Some Exemplary Multiply Charged Cationic Polyamines for Destroying Emulsions in Production Fluids The effectiveness of some exemplary multiply charged cationic compounds was tested using production fluids from three different sites. The sample IDs and structures of the exemplary multiply charged cationic compounds are listed in Table 2. [Table 3]

[0315] The effectiveness of REB is usually measured under simulation conditions that closely match the production site by the emulsion stability of the production fluid to which a specific concentration of REB is added.

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

[0317] The bottle test was conducted using a high-temperature bottle test instrument. This bottle test instrument can achieve high-temperature and high-pressure conditions that are compatible with conventional methods for oil / water separation at any specific production site. The bottle test instrument is a very simple processing system and does not accurately reproduce what occurs within a complex processing system that uses separators, washing tanks, heater treaters, etc. in an oil production facility, but it enables comparison of the test results with those in the facility. For example, if the oil exiting the processing system contains only 0.5% BS&W (bitumen, solids, and water emulsion), the oil analysis from the bottle test for REB should also be close to this result.

[0318] Since each customer's equipment, its layout, distance, temperature, and chemical injection points are different, there are no standard bottle test conditions. However, the bottle test instrument used in this example can adjust the chemical ratio, agitation, temperature, and settling time to conform to the conditions of the production facility.

[0319] The production fluid was collected from the customer's process for use in this example. Although some aging of the sample occurred, in this operation, the time to transfer to the bottle and start the test was minimized to reduce the variation in the results. Diluent samples were collected and used over several days.

[0320] For the bottle test, a sample of about 100 ml was added to the bottle. Then, EB was injected into the bottle (at a rate based on oil cut), the bottle was sealed and placed in the bottle test equipment. Then, the sample was heated to a temperature such as 140 °C and the bottle was shaken using a mechanical shaker. REB and diluent were injected into the bottle and various shaking steps were completed. Droplet readings were taken over a predetermined time and recorded in mL. Then, a sample of the upper 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 (trademark)). The mixture was shaken well to mix and then centrifuged. Then, BS&W was measured. The water quality was examined using various techniques including visual inspection and turbidity. Usually, for the composite material sample, the emulsion was measured by removing the free water, gently mixing, and then transferring it to a centrifuge tube with xylene, toluene, or light oil (e.g., Varsol (trademark)). The sample was shaken well to mix and then centrifuged, and BS&W was recorded.

[0321] The transparency of water was ranked on a comparative appearance scale of 11 (partially disrupted) to 1 (about 50 NTU). A rating of 9 can be considered equivalent to 1500 NTU, and a rating of 4 or 5 is equal to about 500 NTU.

[0322] The test results for exemplary multi-charged polyamines and some existing REBs are shown in Tables 4, 5, and 6A - 6B for tests at three different sites respectively. In Tables 4, 5, and 6A - 6B, G = Good, F = Fair, P = Poor, VP = Very Poor. “+” or “-” are additional qualifiers 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-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 100 g) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, triethylenetetramine (TETA, 60%, 15 g) was 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%. For the application test, the obtained aqueous solution of Compound 7 was used as it was.

[0324] Example 9 Synthesis of Multiply Charged Cationic Compound 8 (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 216 g) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, tris(2-aminoethyl)amine (95%, 216 g) was 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%. For the application test, the obtained aqueous solution of Compound 8 was used as it was.

[0325] Example 10 Synthesis of Multiply Charged Cationic Compound 9 (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 199 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, ethylenediamine (EDA, 99%, 11 grams) was 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%. For the application test, the obtained aqueous solution of Compound 9 was used as it was.

[0326] Example 11 Synthesis of Multiply Charged Cationic Compound 10 Sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS, 58%, 94 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, diethylenetriamine (DETA, 99%, 5 grams) was 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%. For the application test, the obtained aqueous solution of Compound 10 was used as it was.

[0327] Example 12 Synthesis of Multiply Charged Cationic Compound 11 Sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS, 58%, 70 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, triethylenetetraamine (TEPA, 99%, 5 grams) was 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%. For the application test, the obtained aqueous solution of Compound 11 was used as it was.

[0328] Example 13 Synthesis of Multiply Charged Cationic Compound 12 Sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS, 58%, 50 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, ethylenediamine (99%, 50 grams) was 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%. For the application test, the obtained aqueous solution of Compound 12 was used as it was.

[0329] Example 14 Synthesis of Multiply Charged Cationic Compound 13 Sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS, 58%, 9.5 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, tris(2-aminoethyl)amine (95%, 145 grams) was 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%. For the application test, the obtained aqueous solution of Compound 13 was used as it was.

[0330] Example 15 Synthesis of Multiply Charged Cationic Compound 14 A solution of sodium vinyl sulfonate (NaVS, 25%, 152 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, diethylenediamine (99%, 6 grams) was 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%. For the application test, the obtained aqueous solution of Compound 14 was used as it was.

[0331] Example 16 Synthesis of Multiply Charged Cationic Compound 15 A solution of sodium vinyl sulfonate (NaVS, 25%, 113 grams) was charged into a 250 mL three-necked RBF equipped with a magnetic stir bar, a temperature probe, and a condenser. Then, ethyleneamine E-100 (99%, 9 grams) was 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%. For the application test, the obtained aqueous solution of compound 15 was used as it was.

[0332] Although the present disclosure has been described as such, it will be apparent that the same can vary in many ways. Such variations should not be regarded as a departure from the spirit and scope of the present disclosure, and all such modifications are intended to be included within the scope of the following claims. Examples of embodiments of the present invention are listed in the following items [1] to

[51] . [1] A compound derived from an aza-Michael addition reaction between a polyamine (Michael donor) and an activated olefin (Michael acceptor) having an ionic group according to one of the following formulas: [Chemical formula] In the formula, X is NH or O, R 2 is H, CH3, or an unsubstituted linear or branched C2-C 10 alkyl, alkenyl, or alkynyl group, R 2’ is H, CH3, or an unsubstituted or substituted linear or branched C1-C 10 alkyl, alkenyl, alkynyl group, -COOH, -CH2COOH, Y’, or -(CH2) m -Y’, m is an integer from 2 to 4, R3 is absent or an unsubstituted linear or branched C1-C 30 alkylene group, Y is -NR4R5R6 (+) In the formula, R 4 , R 5 , and R 6independently, C1 to C 10 is an alkyl group, Y’ is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H, 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 NH2-[R 10’ n -NH2, (RNH) n -RNH2, H2N-(RNH) n -RNH2, or H2N-(RN(R’)) n -RNH2, and is a linear, branched, or dendritic polyamine having the general formula, where R 10’ is a linear or branched unsubstituted or substituted C2 to C 10 alkylene group, or a combination thereof, R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4 to C 10 alkylene group, or a combination thereof, R’ is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4 to C 10 alkyl group, RNH2, RNHRNH2, or RN(RNH2)2, and n is 2 to 1,000,000, the compound according to item 1. [3] the polyamine is (i) an unmodified polyamine, (ii) a modified polyamine, (iii) an ethoxylated polyamine, a propylated polyamine, a polyamine having a polyquat, a polyamine having a polyglycerol, or a combination thereof, or (iv) a linear, branched, or dendritic polyethyleneimine, the compound according to item 1 or 2. [4] the polyamine contains (i) only primary and secondary amine groups, (ii) only primary, secondary, and tertiary amine groups, or (iii) only primary and tertiary amine groups, the compound according to any one of items 1 to 3.​ [5] wherein the polyamine is (i) NH2-[R 10’ n -NH2 (wherein R 10’ is a linear or branched unsubstituted or substituted C2-C 10 alkylene group, or a combination thereof), (ii) (RNH) n -RNH2 or H2N-(RNH) n -RNH2 (wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof), or (iii) H2N-(RN(R’)) n -RNH2 (wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4-C 10 alkylene group, or a combination thereof, and R’ is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, a linear or branched unsubstituted or substituted C4-C 10 alkyl group, RNH2, RNHRNH2, or RN(RNH2)2), and is a polyamine having the general formula, the compound according to any one of items 1 to 4. [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 (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethane-1-aminium methyl sulfate (DMAEA-MSQ), or 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MSQ), or (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 a mixture thereof, and is the compound according to any one of items 1 to 5. [7] The polyamine has an average molecular weight (M w ) of about 60 to about 2,000,000 Da, or about 60 to about 5,000 Da, and is the compound according to any one of items 1 to 6. [8] 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, and is the compound according to any one of items 1 to 7. [9] The compound according to any one of items 1 to 8, wherein the compound has an average molecular weight of about 100 to about 2,000,000 Da, or about 100 to about 5,500 Da.

[10] The compound according to any one of items 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

Chemical formula

[12] The compound is

Chemical formula

[13] The compound is derived from polyethyleneimine and (3-acrylamidopropyl) trimethylammonium chloride (APTAC), the polyethyleneimine is linear PEI, and has an average molecular weight (M w ) of about 5,000, the compound according to item 1.

[14] The compound is derived from polyethyleneimine and (3-acrylamidopropyl) trimethylammonium chloride (APTAC), the polyethyleneimine is linear PEI, and has an average molecular weight (M w ) of about 750,000, the compound according to item 1.

[15] The compound is derived from polyethyleneimine and (3-acrylamidopropyl) trimethylammonium chloride (APTAC), the polyethyleneimine is branched PEI, and has an average molecular weight (M wThe compound according to item 1, having

[16] The compound according to any one of items 1 to 15, wherein the compound is water-soluble.

[17] A method for synthesizing a compound, comprising contacting an activated olefin having a cationic group with a polyamine to produce the compound, wherein the activated olefin is of one of the following formulas,

Chemical formula

[18] The method according to item 17, wherein the contacting step is carried out in the presence of a reaction solvent, a reaction solvent and an alkali source, a reaction solvent and an acid, or a reaction solvent and a catalyst.

[19] The method according to item 18, wherein the reaction solvent is water, methanol, ethanol, propanol, glycol, PEG, or a mixture thereof.

[20] The method according to item 18, wherein the contacting step is carried out in the presence of benzyltrimethylammonium hydroxide.

[21] The method according to item 18, wherein the contacting step is carried out without an acid, a base, an alkali source, or a catalyst.

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

[23] The article, product, or composition according to item 22, wherein the article, product, or composition further comprises a carrier.

[24] The article, product, or composition according to item 22 or 23, wherein the article, product, or composition is an aqueous article, product, or composition.

[25] The article, product, or composition according to item 22 or 23, wherein the carrier is water, alcohol, alkylene glycol, alkylene glycol alkyl ether, or a combination thereof.

[26] The article, product, or composition according to any one of items 22 to 25, further comprising an additional surfactant, wherein the additional surfactant is nonionic, semi-nonionic, cationic, anionic, amphoteric, zwitterionic, gemini, surfactant, or a mixture thereof.

[27] A method for decomposing an inverse emulsion in a production fluid 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 produce a treated production fluid. The inverse emulsion breaking composition comprises one or more compounds or salts thereof according to any one of items 1 to 16, and one or more additional inverse emulsion breaking composition agents, a method.

[28] The method according to item 27, wherein the inverse emulsion breaking composition breaks an oil-in-water emulsion in the production fluid.

[29] The method according to item 27 or 28, wherein the production fluid comprises an oil-in-water emulsion, a water-in-oil-in-water emulsion, or both.

[30] The production fluid is (i) from a steam-assisted gravity drainage (SAGD) process, comprising crude oil, refined oil, bitumen, condensate, waste oil, distillate, fuel, or a mixture thereof, the production fluid comprising bitumen and water, or (iii) associated water, the associated water being the water portion of the production fluid after removal of oil and dirt, the method according to item 27 or 28.

[31] The method according to any one of items 27 to 30, wherein the compound has 3 to 100, or 3 to 15 average net charges.

[32] The method according to any one of items 27 to 31, wherein the REB composition further comprises a carrier, and the carrier is water, alcohol, alkylene glycol, alkylene glycol alkyl ether, or a combination thereof.

[33] The method according to item 32, wherein the carrier is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

[34] The method according to any one of items 27 to 33, wherein the REB composition further comprises one or more of the additional inverse emulsion breaking composition agents.

[35] The method according to any one of items 27 to 34, wherein the REB composition contains about 30% to about 70% by weight of the compound or a salt thereof.

[36] The method according to any one of items 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] The method according to any one of items 27 to 36, further comprising contacting the production fluid with an emulsion breaker or an additional reverse emulsion breaker (REB) agent, wherein the emulsion breaker or the additional REB agent contacts the production fluid independently, simultaneously, or sequentially.

[38] The method according to item 37, wherein the emulsion breaker or the additional REB agent contacts the production fluid by means of a compound in the REB composition or through another composition.

[39] The additional REB agent is

Chemical formula

[40] The method according to item 37 or 38, wherein the emulsion breaker or the additional REB agent is another polymeric cationic, anionic, non-ionic, inorganic coagulant / coagulant, or an oxyalkylated phenol-formaldehyde resin, resin ester, oxyalkylated polyalkylamine, polyol, crosslinked polyol having a bifunctional or polyfunctional crosslinking agent, isocyanate, acid, or a combination thereof.

[41] The method according to item 37 or 38, wherein the emulsion breaker or the additional REB agent comprises a dendritic polyamine, dendritic polyamidoamine, hyperbranched polyethyleneimine, reaction products thereof with gluconolactone, alkylene oxide, 3-chloro-2-hydroxypropanesulfonic acid, alkyl halide, benzyl halide, and dialkyl sulfate, or mixtures thereof.

[42] The method according to item 37 or 38, wherein the emulsion breaker or the additional REB agent comprises a polyepihalohydrin, its polyelectrolyte, trithiocarbamic acid, dithiocarbamate, dimethylaminoethyl acrylate methyl chloride, benzyl chloride quaternary salt, polymeric quaternary ammonium betaine, metal salt, zinc chloride, aluminum chloride, polymeric quaternary ammonium salt, copolymer of acrylic acid and acrylamide, or mixtures thereof.

[43] The emulsion breaker or the additional REB agent is a high molecular weight polymeric cationic coagulant / coagulant, and the high molecular weight polymeric cationic coagulant / coagulant has an average molecular weight (M w ) of 100,000 to 2,000,000 Da, and the high molecular weight polymeric cationic coagulant / coagulant has an average net charge of 10 to 1,000, the method according to item 37 or 38.

[44] The emulsion breaker or the additional REB agent is a low molecular weight polymeric cationic coagulant / flocculant, the low molecular weight polymeric cationic coagulant / flocculant has an average molecular weight of 10,000 to 100,000 Da, and the low molecular weight polymeric cationic coagulant / flocculant has 3 to 10 net charges. The method according to item 37 or 38.

[45] 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 has a molecular weight of 100,000 to 2,000,000, and the high molecular weight polymeric anionic coagulant / flocculant has 10 to 1,000 net charges. The method according to item 37 or 38.

[46] The emulsion breaker or the additional REB agent is a low molecular weight polymeric anionic coagulant / flocculant, the low molecular weight polymeric cationic coagulant / flocculant has a molecular weight of 10,000 to 100,000, and the low molecular weight polymeric anionic coagulant / flocculant has 3 to 10 net charges. The method according to item 37 or 38.

[47] The emulsion breaker or the additional REB agent is a high molecular weight polymeric nonionic coagulant / flocculant, the high molecular weight polymeric nonionic coagulant / flocculant has a molecular weight of 100,000 to 2,000,000, or a low molecular weight polymeric nonionic coagulant / flocculant, and the low molecular weight polymeric nonionic coagulant / flocculant has a molecular weight of 10,000 to 100,000. The method according to item 37 or 38.

[48] The reverse emulsion breaking composition further comprises a diluent. The method according to any one of items 27 to 47.

[49] The method further comprises separating oil and solids from water in the treated production fluid via filtration, sedimentation, desalination, electrochemical techniques, centrifugation, flotation, or a combination thereof. The method according to any one of items 27 to 47.

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

[51] The reverse emulsion breaking composition according to Item 50, wherein the reverse emulsion breaking composition breaks an oil-in-water emulsion in the production fluid.

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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