Synergistic Solvents for Crude Oil Emulsion Breakers

Abstract

The present disclosure relates to demulsifier compositions containing one or more demulsifying polymers and an alkyl carboxylic acid solvent, and methods of using the compositions to separate water-in-oil emulsions.

Description

[Technical field]

[0001] Priority claim This application claims priority to U.S. Patent Application No. 17 / 550,804, filed December 14, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure describes a wet crude oil emulsion demulsifier composition containing a solvent and a demulsifying polymer, the solvent and the demulsifying polymer exhibit a synergistic effect, and the demulsifier composition is effective in demulsifying the wet crude oil emulsion. [Background technology]

[0003] Crude oil is typically extracted with varying concentrations of dispersed water. Water-in-oil (W / O) emulsions are believed to initially form during the migration of oil and water through the porous reservoir rock to the production well and then during transportation to the production facility for phase separation. Further emulsification of water and oil can occur due to pressure drops across choke valves in the production headers used to manage the production flow, which introduces significant agitation and turbulence energy.

[0004] The dispersed water droplets are stabilized by surface active compounds (surfactants) naturally present in the oil, such as resins, asphaltenes, solid particles, organic acids and organic bases. These surfactants migrate to the oil-water interface and form films around the water droplets, slowing the natural process of coalescence between the droplets. The film greatly influences whether the emulsion separates easily (loose emulsion) or does not separate spontaneously (tight emulsion). Tight emulsions require significant investment by oil companies in processes and chemical interventions to separate or break the emulsion in order to produce crude oil within export specifications of 0.2% by volume basic sediment and water (BS&W) and 10 pounds total dissolved salts per thousand barrels (PTB). Thus, the composition of crude oil can vary significantly from one producing field to another, resulting in different combinations of these parameters with unique effects. In some particularly dense oil emulsions, the water cannot be separated by physical methods alone, such as retention, heating, and electrical coalescence. In such cases, a combination of physical and chemical methods is required to achieve the desired water separation.

[0005] In crude oil production facilities, it is necessary to quickly and efficiently separate water from W / O emulsions to produce wet crude oil, which can then be sent for further refining (desalting and dehydration). Formulations or compositions containing compounds called demulsifiers or demulsifying polymers and solvents have been used to break such crude oil-water emulsions. Having a high-performance demulsifying formulation (e.g., rapid and capable of dehydrating large quantities) allows for the production of more on-spec dry crude oil as well as better control of the overall process (e.g., dehydrator load).

[0006] Therefore, there is a need for a demulsifier composition that is faster and more efficient at dehydrating wet crude oil emulsions than known demulsifier compositions. Summary of the Invention

[0007] In the present disclosure, a demulsifier composition is provided. In some embodiments, the demulsifier composition includes a demulsifying polymer; and a solvent. In some embodiments, the solvent has an alkyl chain of 1 to 8 carbon atoms, a pKa of about 2 to about 7, and a K of greater than about 0.1. ow It is an alkyl carboxylic acid having the formula:

[0008] In some embodiments, the demulsifying polymer is an alkoxylated phenolic polymer or an alkoxylated polyalcohol. In some embodiments, the alkoxylated phenolic polymer is para-substituted with a saturated hydrocarbon chain. In some embodiments, the saturated hydrocarbon chain is selected from para-tertiary-alkyl, para-secondary-alkyl, para-iso-alkyl, para-cycloalkyl, and para-n-alkyl. In some embodiments, the saturated hydrocarbon chain is selected from para-tertiary-butylphenol, para-tertiary-amylphenol, para-tertiary-hexylphenol, and para-tertiary-heptylphenol.

[0009] In some embodiments, the alkoxylated phenolic polymer has the structure: [ka] It has wherein R is a saturated hydrocarbon chain having 1 to 8 carbons; R′ and R″ are each independently selected from H and C1-C2 alkyl; wherein the total number of carbon atoms in R, R′, and R″ is 3 to 8; PPO is a compound having the formula: [ka] and PEO is a polypropylene oxide having the formula: [ka] wherein x is an integer from 0 to 10; y is an integer from 0 to 10; and n is an integer from 3 to 10.

[0010] In some embodiments, the demulsifying polymer has the structure: [ka] has.

[0011] In some embodiments, the demulsifying polymer has the structure: [ka] has.

[0012] In some embodiments, the demulsifier composition contains about 25% to about 50% by weight of the demulsifying polymer.

[0013] In some embodiments, the demulsifier composition contains about 20% to about 60% by weight of a solvent.

[0014] In some embodiments of the demulsifier composition, the alkyl chain of the alkyl carboxylic acid is linear or branched.

[0015] In some embodiments of the demulsifier composition, the pKa is from about 3 to about 6.

[0016] In some embodiments of the demulsifier composition, the alkyl carboxylic acid has a melting point of about 15° C. or less. In some embodiments, the alkyl carboxylic acid has a melting point of about 10° C. or less.

[0017] In some embodiments of the demulsifier composition, the alkyl carboxylic acid has a boiling point of about 80° C. or greater. In some embodiments, the alkyl carboxylic acid has a boiling point of about 90° C. or greater.

[0018] In some embodiments of the demulsifier composition, the solvent comprises an alkyl group having an alkyl chain of 1 to 8 carbon atoms, a pKa of about 2 to about 7, a K of greater than about 0.1, ow , an alkyl carboxylic acid having a melting point below about 15°C and a boiling point above about 80°C.

[0019] In some embodiments of the demulsifier composition, the solvent has an alkyl chain of 1 to 8 carbon atoms, a pKa of about 3 to about 6, a K of greater than about 0.1 ow , an alkyl carboxylic acid having a melting point below about 10°C and a boiling point above about 90°C.

[0020] In some embodiments, the demulsifier composition further comprises a clarifying agent. In some embodiments, the clarifying agent is selected from 1,2,4-trimethylbenzene, naphthalene, and combinations thereof. In some embodiments, the clarifying agent comprises from about 0.1% to about 10% by weight of the demulsifier composition.

[0021] A method for dehydrating a water-in-oil emulsion is also provided in the present disclosure. In some embodiments, the method comprises adding a demulsifier composition of the present disclosure to a water-in-oil emulsion and separating the water from the emulsion. In some embodiments, the water-in-oil emulsion is a crude oil emulsion. In some embodiments, the crude oil emulsion is a refinery desalted emulsion. In some embodiments, the crude oil emulsion is a crude oil production emulsion.

[0022] Methods for treating produced petroleum containing emulsions are also provided in the present disclosure. In some embodiments, the methods include contacting the produced petroleum containing emulsions with a demulsifier composition of the present disclosure to reduce or eliminate the emulsions. [Brief description of the drawings]

[0023] [Figure 1] 1 is a graph showing the water separation performance at 30° C. of 50 ppm demulsifier compositions prepared from various solvents. [Diagram 2] FIG. 1 shows the water separation performance versus water coefficient partitioning (Kow) of demulsifier compositions prepared from various solvents. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] Reference will now be made in detail to particular embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the illustrated subject matter is not intended to limit the claims to the disclosed subject matter.

[0025] Due to many factors involved in the manufacturing process, oil and water mix and create an emulsion. This is undesirable when refining crude oil, as the crude should be as dry as possible, as water can damage the refinery, induce corrosion, and reduce the efficiency of the crude distillation process. In the present disclosure, a demulsifier composition is provided that can be used to break crude oil-water emulsions. The demulsifier composition of the present disclosure contains a demulsifying polymer and a solvent, such as a solvent described in the present disclosure. In some embodiments, the solvent is an acid. In some embodiments, the solvent is a linear or branched chain alkyl carboxylic acid, the alkyl chain having 1 to 8 carbon atoms. In some embodiments, the solvent has a melting point of less than about 15° C., such as less than about 10° C. In some embodiments, the solvent has a pKa of about 2 to about 7, such as about 3 to about 6. In some embodiments, the solvent has a K of greater than about 0.1. ow (partition coefficient between n-octanol and water). In some embodiments, the solvent has a boiling point greater than about 80° C., such as a boiling point greater than about 90° C. In some embodiments, the solvent is non-toxic, not highly flammable, or both. In some embodiments, the demulsifier composition contains a clarifier.

[0026] In some embodiments, the demulsifier compositions of the present disclosure exhibit improved water separation performance compared to other demulsifier compositions that do not contain the solvent of the present disclosure. In some embodiments, the demulsifier compositions of the present disclosure separate water from oil more quickly than other demulsifier compositions that do not contain the solvent of the present disclosure. In some embodiments, the demulsifier compositions of the present disclosure are more efficient at dehydrating wet crude oil emulsions than other demulsifier compositions that do not contain the solvent of the present disclosure. For example, the demulsifier compositions of the present disclosure allow for the dehydration of larger amounts of water than other demulsifier compositions, such as those that contain a different solvent than those described in this disclosure. In some embodiments, the solvent-containing demulsifier compositions of the present disclosure are more efficient at water separation compared to compositions that contain known demulsifier solvents, such as methanol, diethylene glycol, xylene, etc.

[0027] The demulsifier composition of the present disclosure has been shown to be faster and more efficient at separating water from wet crude oil emulsions than other demulsifier compositions containing a different solvent than that of the present disclosure. Thus, the present disclosure provides a method for separating water from wet crude oil emulsions, comprising adding the demulsifier composition of the present disclosure to the emulsion. In some embodiments, the demulsifier composition breaks a stable emulsion. In some embodiments, the demulsifier composition is used in water-in-crude oil emulsions during oil field production at a gas-oil separation plant (GOSP). In some embodiments, the demulsifier composition is used to desalt water-in-crude oil emulsions at a refinery.

[0028] Without wishing to be bound by any particular theory, it is believed that the particular combination of properties of the solvents described in this disclosure results in unexpected improvements in water separation.

[0029] definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs. Methods and materials for use in this application are described herein; other suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and are not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, controls.

[0030] Values ​​expressed in range format should be interpreted flexibly to include not only the numerical values ​​explicitly recited as the limits of the range, but also to include all individual numerical values ​​or subranges subsumed within the range, as if each numerical value and subrange were explicitly recited. For example, the range "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also the individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the range recited. "About X to Y" is synonymous with "about X to about Y" unless otherwise specified. Similarly, the description "about X, Y, or about Z" is synonymous with "about X, about Y, or about Z" unless otherwise specified.

[0031] The term "about" as used in this disclosure may allow for some variation in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or the limits of a stated range.

[0032] As used in this disclosure, the terms "a," "an," and "the" are used to include one or more than one, unless the context clearly dictates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise specified. The phrase "at least one of A and B" is synonymous with "A, B, or A and B." Furthermore, it should be understood that any phrases or terms used in this disclosure that are not otherwise defined are for descriptive purposes only and not for limiting purposes. Any use of section headings is intended to aid in the reading of the document and should not be construed as limiting. Information associated with a section heading may occur within or outside that particular section.

[0033] In the methods disclosed herein, operations may be performed in any order unless a chronological or operational order is explicitly recited. Moreover, specified operations may be performed simultaneously unless express claim language dictates that they be performed separately. For example, a claimed operation of doing X and a claimed operation of doing Y may be performed simultaneously in a single operation, with the resulting process falling within the literal scope of the claimed process.

[0034] "Demulsifiers", also known as "emulsion breakers", are chemicals used to separate crude oil from water. Demulsifiers are chemicals designed to neutralize the stabilizing effect of emulsifiers. Demulsifiers are surface active compounds that, when added to an emulsion, migrate to the oil / water interface, rupture or weaken the rigid film, and promote the coalescence of the water droplets. The process of separating oil and water emulsions is known as "demulsification" and can be accomplished in a variety of ways, including the addition of chemical demulsifiers to the emulsion. In some embodiments, the demulsifier is a polymer, referred to herein as a "breaking polymer".

[0035] "Dehydration," as used herein, is the process of removing or separating water from crude oil. In some embodiments, water is removed or separated from an emulsion that is a water-in-oil emulsion.

[0036] As used in this disclosure, the term "subsurface formation" can refer to any material below the surface of the Earth, including below the surface of the bottom of the ocean. For example, a subsurface formation or material can be any section of a well bore and any section of a formation or region that produces subsurface petroleum or groundwater in fluid contact with the well bore. Placing a material in a subsurface formation can include contacting the material with any section of a well bore or any subsurface region in fluid contact with the well bore. Subsurface materials can include any material that is placed in a well bore, such as cement, drill shafts, liners, tubing, casing, or screens. Placing a material in a subsurface formation can include contacting such subsurface materials. In some examples, a subsurface formation or material can be a subsurface region capable of producing liquid or gaseous petroleum material, water, or any section below the ground in fluid contact with liquid or gaseous petroleum material or water. In some embodiments, a subsurface formation is an oil well.

[0037] Demulsifier Composition In accordance with the present disclosure, there is provided a demulsifier composition comprising a demulsifying polymer and an alkyl carboxylic acid solvent, the alkyl carboxylic acid having an alkyl chain containing 1 to 8 carbon atoms and a carboxylic acid functionality, a pKa of about 2 to about 7, and a K of greater than 0.1. ow The demulsifier compositions can be used to dehydrate wet crude oil emulsions. In some embodiments, compositions containing the demulsifying polymers and solvents of the present disclosure are more efficient and faster at dehydrating wet crude oil emulsions compared to compositions that do not contain the solvents of the present disclosure but contain other known demulsifying solvents.

[0038] Demulsifying Polymer The demulsifier composition of the present disclosure contains a demulsifying polymer. Any demulsifying polymer known to those skilled in the art can be used in the demulsifier composition of the present disclosure. Examples of suitable demulsifying polymers include, but are not limited to, alkoxylated polyalcohols, alkoxylated polyglycols, and alkoxylated phenols. In some embodiments, the demulsifying polymer is an alkoxylated phenol polymer or an alkoxylated polyalcohol.

[0039] In some embodiments, the demulsifying polymer is an alkoxylated phenolic polymer. The alkoxylated phenolic polymer is composed of a formaldehyde-phenolic backbone and lipophilic polypropylene oxide (PPO) sections and hydrophilic polyethylene oxide (PEO) sections, the formaldehyde-phenolic backbone being composed of phenols para-substituted with saturated hydrocarbon chains. In some embodiments, the saturated hydrocarbon chains contain 4-9 carbons, such as 4-8, 4-7, 4-6, 5-9, 5-8, 5-7, 6-9, 6-8, 7-9, or 4, 5, 6, 7, 8, or 9 carbons. In some embodiments, the alkoxylated phenolic polymer is para-substituted with saturated hydrocarbon chains. In some embodiments, the saturated hydrocarbon chains are selected from para-tertiary-alkyl, para-secondary-alkyl, para-iso-alkyl, para-cycloalkyl, and para-n-alkyl. In some embodiments, the saturated hydrocarbon chain is selected from para-tertiary-butylphenol, para-tertiary-amylphenol, para-tertiary-hexylphenol, and para-tertiary-heptylphenol. In some embodiments, the demulsifying polymer has a hydrocarbon chain composed of a propane segment substituted at the 2-position (the middle of the propane chain) with a saturated alkyl group. Examples of suitable demulsifying polymers include those disclosed in U.S. Pat. Nos. 2,499,370 and 2,557,081, each of which is incorporated by reference in its entirety.

[0040] In some embodiments, the demulsifying polymer has the structure: [ka] is a compound having the formula During the ceremony, R is a saturated carbon chain having 1 to 8 carbons; R' and R'' are each independently selected from H and C1-C2 alkyl; wherein the total number of carbon atoms in R, R', and R'' is between 3 and 8; PPO has the formula: [ka] is a polypropylene oxide having the formula: PEO has the formula: [ka] is a polyethylene oxide having the formula: x is an integer from 0 to 10; y is an integer from 0 to 10; and n is an integer from 3 to 10.

[0041] In some embodiments, R is a saturated hydrocarbon (alkyl) chain having 1 to 8 carbon atoms, e.g., 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 4 to 8, 4 to 7, 4 to 6, 5 to 8, 5 to 7, and 6 to 8 carbon atoms. In some embodiments, R is an alkyl chain having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. In some embodiments, the alkyl chain is linear. In some embodiments, the alkyl chain is branched. In some embodiments, the alkyl chain has an iso-, neo-, or anteiso-branching pattern.

[0042] In some embodiments, R' and R'' are each independently selected from H and C1-C2 alkyl. In some embodiments, R' and R'' are each independently selected from H and methyl. In some embodiments, R' and R'' are each H. In some embodiments, R' and R'' are each C1-C2 alkyl. In some embodiments, R' and R'' are each methyl. In some embodiments, R' and R'' are each ethyl. In some embodiments, the demulsifying polymer has a 2-iso-alkyl-propyl group substituted on the phenolic backbone at the para position.

[0043] In some embodiments, the total number of carbon atoms in R, R', and R'' is 3-8, e.g., 3-7, 3-6, 3-5, 4-8, 4-7, 4-6, 5-9, 5-8, 5-7, 6-9, 6-8, 7-9, or 3, 4, 5, 6, 7, 8, or 9. In some embodiments, R is an alkyl chain having 1-8 carbon atoms. In some embodiments, R is an alkyl chain having 1-8 carbon atoms, R' is a C1-C2 alkyl, and R'' is a C1-C2 alkyl. In some embodiments, R is an alkyl chain having 1-8 carbon atoms, R' is methyl, and R'' is methyl. In some embodiments, R is an alkyl chain having 3-8 carbon atoms, R' is H, and R'' is H.

[0044] In some embodiments, PPO, i.e., polypropylene oxide, has the formula: [ka] In the formula, x is an integer from 0 to 10, for example, 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 4 to 10, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 5 to 10, 5 to 9, 5 to 8, 5 to 7, 6 to 10, 6 to 9, 6 to 8, 7 to 10, 7 to 9, and 8 to 10. In some embodiments, x is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0045] In some embodiments, PEO, or polyethylene oxide, has the formula: [ka] In the formula, y is an integer of 0 to 10, for example, 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 4 to 10, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 5 to 10, 5 to 9, 5 to 8, 5 to 7, 6 to 10, 6 to 9, 6 to 8, 7 to 10, 7 to 9, and 8 to 10.

[0046] In some embodiments, x and y are the same. In some embodiments, x and y are different.

[0047] In some embodiments, the phenolic backbone of the demulsifying polymer is composed of repeating phenolic units linked via methylene linkers, in some embodiments, n is an integer from 3 to 10, such as 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 4 to 10, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 5 to 10, 5 to 9, 5 to 8, 5 to 7, 6 to 10, 6 to 9, 6 to 8, 7 to 10, 7 to 9, and 8 to 10.

[0048] In some embodiments of the demulsifier composition of the present disclosure, the demulsifying polymer has the structure: [ka] It has where R, x, y, and n are as disclosed in the present application.

[0049] In some embodiments of the demulsifier composition of the present disclosure, the demulsifying polymer has the structure: [ka] has.

[0050] In some embodiments, the demulsifier composition contains from about 25% to about 50% by weight of the demulsifier polymer, e.g., from about 25% to about 45% by weight, from about 25% to about 40% by weight, from about 25% to about 35% by weight, from about 25% to about 30% by weight, from about 30% to about 50% by weight, from about 30% to about 45% by weight, from about 30% to about 40% by weight, from about 30% to about 35% by weight, from about 35% to about 50% by weight, from about 35% to about 45% by weight, from about 35% to about 40% by weight, from about 40% to about 50% by weight, from about 40% to about 45% by weight, from about 45% to about 50% by weight, or about 25% by weight, about 30% by weight, about 35% by weight, about 37% by weight, about 39% by weight, about 40% by weight, about 45% by weight, or about 50% by weight. In some embodiments, the demulsifier composition contains about 35% to about 45% by weight of the demulsifying polymer. In some embodiments, the demulsifier composition contains about 37% to about 40% by weight of the demulsifying polymer. In some embodiments, the demulsifier composition contains about 37% by weight of the demulsifying polymer. In some embodiments, the demulsifier composition contains about 39% by weight of the demulsifying polymer. In some embodiments, the demulsifier composition contains about 40% by weight of the demulsifying polymer.

[0051] solvent The demulsifier compositions of the present disclosure contain a solvent, the solvent being an alkyl carboxylic acid having an alkyl chain of 1 to 8 carbon atoms and a carboxylic acid functional group. Without wishing to be bound by any particular theory, it is believed that it is a combination of properties and characteristics of the solvent, such as the properties and characteristics described in this disclosure, that result in the ability to efficiently separate water from wet crude oil emulsions, as compared to other solvents used in known demulsifier compositions. In some embodiments, it is the combination of alkyl chain length, carboxylic acid functional group, melting point, boiling point, pKa and K that result in the ability to efficiently separate water from wet crude oil emulsions, as compared to other solvents used in known demulsifier compositions. ow In some embodiments, the combination of the solvent and the demulsifying polymer provides a synergistic effect in demulsifying the wet crude oil emulsion.

[0052] In some embodiments, the solvents described herein are alkyl carboxylic acids having an alkyl chain of 1-8 carbon atoms and a carboxylic acid functional group. In some embodiments, the alkyl chain has 1-8 carbon atoms, e.g., 1-7, 1-6, 1-5, 1-4, 1-3, 2-8, 2-7, 2-6, 2-5, 2-4, 3-8, 3-7, 3-6, 3-5, 4-8, 4-7, 4-6, 5-8, 5-7, 6-8, or 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. In some embodiments, the alkyl chain has 1 carbon atom. In some embodiments, the alkyl chain has 2 carbon atoms. In some embodiments, the alkyl chain has 3 carbon atoms. In some embodiments, the alkyl chain has 4 carbon atoms. In some embodiments, the alkyl chain has 5 carbon atoms. In some embodiments, the alkyl chain has 6 carbon atoms. In some embodiments, the alkyl chain has 7 carbon atoms. In some embodiments, the alkyl chain has 8 carbon atoms. In some embodiments, the alkyl chain is linear. In some embodiments, the alkyl chain is branched. In some embodiments, the alkyl chain has a branching pattern including, but not limited to, iso-, neo-, anteiso-, and 2-alkyl-2-propyl groups.

[0053] In some embodiments, the alkyl carboxylic acid solvent described herein has a melting point that allows the solvent to be liquid at operating temperatures typically found in subterranean formations. In some embodiments, the operating temperature is from about 30° C. to about 70° C. Thus, in some embodiments, the solvent has a melting point of less than about 30° C., such as less than about 25° C., less than about 20° C., less than about 15° C., less than about 10° C., or less. In some embodiments, the solvent has a melting point of less than about 10° C. to less than about 15° C. In some embodiments, the solvent has a melting point of less than about 15° C. In some embodiments, the solvent has a melting point of less than about 10° C.

[0054] In some embodiments, the alkyl carboxylic acid solvent described in this disclosure has a boiling point such that the solvent does not substantially evaporate at operating temperatures typically found in subterranean formations. In some embodiments, the operating temperature is from about 30°C to about 70°C. Thus, in some embodiments, the solvent has a boiling point greater than about 70°C, e.g., greater than about 75°C, greater than about 80°C, greater than about 85°C, greater than about 90°C, or higher. In some embodiments, the solvent has a boiling point greater than about 80°C to about 90°C. In some embodiments, the solvent has a boiling point greater than about 80°C. In some embodiments, the solvent has a boiling point greater than about 90°C.

[0055] In some embodiments, the alkyl carboxylic acid solvent described herein may be from about 2 to about 7, e.g., from about 2 to about 6.5, from about 2 to about 6, from about 2 to about 5.5, from about 2 to about 5, from about 2 to about 4.5, from about 2 to about 4, from about 2 to about 3.5, from about 2 to about 3, from about 2 to about 2.5, from about 2.5 to about 7, from about 2.5 to about 6.5, from about 2.5 to about 6, from about 2.5 to about 5.5, from about 2.5 to about 5, from about 2.5 to about 4.5, from about 2.5 to about 4, from about 2.5 to about 3.5, from about 2.5 to about 3, from about 3 to about 7, from about 3 to about 6.5, from about 3 to about 6, from about 3 to about 5.5, from about 3 to about 5, from about 3 to about 4.5, from about 3 to about 4, from about 3 to about 3.5, from about 3.5 to about 7, from about 3.5 to about 6 .5, about 3.5 to about 6, about 3.5 to about 5.5, about 3.5 to about 5, about 3.5 to about 4.5, about 3.5 to about 4, about 4 to about 7, about 4 to about 6.5, about 4 to about 6, about 4 to about 5.5, about 4 to about 5, about 4 to about 4.5, about 4.5 to about 7, about 4.5 to about 6.5, about 4.5 to about 6, about 4.5 to about 5.5, about 4.5 The pKa of the alkyl carboxylic acid solvent described herein is about 5, about 5 to about 7, about 5 to about 6.5, about 5 to about 6, about 5 to about 5.5, about 5.5 to about 7, about 5.5 to about 6.5, about 5.5 to about 6, about 6 to about 7, about 6 to about 6.5, about 6.5 to about 7, or about 3, about 3.5, about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, or about 7. In some embodiments, the alkyl carboxylic acid solvent described herein has a pKa of about 3 to about 6. In some embodiments, the alkyl carboxylic acid solvent described herein has a pKa of about 4 to about 5. The pKa of the solvent is generally about 2 or more, for example, about 2 to about 7. Below a pKa of about 2, the acidity of the solvent may decompose the demulsifying polymer, such as an alkoxylated phenolic polymer, and may corrode equipment (tanks, pumps, pipes). Thus, in some embodiments, the solvent is not a sulfonic acid or a monoester sulfuric acid having an alkyl chain containing 1 to 8 carbon atoms.

[0056] In some embodiments, the alkyl carboxylic acid solvents described in this disclosure are more lipophilic than hydrophilic. This property is expressed by the octanol and water partition coefficient (K ow In some embodiments, the solvents of the present disclosure have a K of greater than about 0.1. owIn some embodiments, the solvent has a K of greater than about 0.3, greater than about 0.5, greater than about 1.0, greater than about 1.25, greater than about 1.5, greater than about 2, greater than about 2.5, greater than about 3, or more. ow has.

[0057] In some embodiments, the alkyl carboxylic acid solvents described in this disclosure are safe to use. In some embodiments, the solvents are non-toxic. In some embodiments, the solvents are not highly flammable.

[0058] Exemplary solvents of the present disclosure include carboxylic acid functional groups and alkyl chains of 1 to 8 carbon atoms, and pKa of about 2 to about 7, K greater than 0.1. ow , a melting point of about 15° C. or less and a boiling point of about 80° C. or more. In some embodiments, the solvent is valeric acid. In some embodiments, the solvent is caprylic acid. In some embodiments, the solvent is acetic acid. In some embodiments, the solvent is propionic acid.

[0059] In some embodiments, the solvent is not a carboxylic acid having a hydroxy group (e.g., lactic acid), a carboxylic acid having one or more aromatic rings, or a carboxylic acid having more than 8 carbons in the alkyl chain, hi some embodiments, the solvent is not pivalic acid.

[0060] In some embodiments, the total amount of solvent in the demulsifier composition is from about 20% to about 60% by weight, e.g., from about 20% to about 55% by weight, from about 20% to about 50% by weight, from about 20% to about 45% by weight, from about 20% to about 40% by weight, from about 20% to about 35% by weight, from about 20% to about 30% by weight, from about 20% to about 25% by weight, from about 25% to about 60% by weight, %, about 25% to about 55%, about 25% to about 50%, about 25% to about 45%, about 25% to about 40%, about 25% to about 35%, about 25% by weight %~about 30 weight%, about 30 weight%~about 60 weight%, about 30 weight%~about 55 weight%, about 30 weight%~about 50 weight%, about 30 weight%~about 45 weight%, about 30 weight%~about 40 weight% , about 30% to about 35% by weight, about 35% to about 60% by weight, about 35% to about 55% by weight, about 35% to about 50% by weight, about 35% to about 45% by weight, about 35% by weight ~40% by weight, approximately 40% by weight ~ approximately 60% by weight, approximately 40% by weight ~ approximately 55% by weight, approximately 40% by weight ~ approximately 50% by weight, approximately 40% by weight ~ approximately 45% by weight, approximately 45% by weight ~ approximately 60% by weight, The total amount of solvent in the demulsifier composition is about 45% to about 55% by weight, about 45% to about 50% by weight, about 50% to about 60% by weight, about 50% to about 55% by weight, about 55% to about 60% by weight, or about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 49% by weight, about 50% by weight, about 52% by weight, about 55% by weight, or about 60% by weight. In some embodiments, the total amount of solvent in the demulsifier composition is about 45% to about 55% by weight. In some embodiments, the total amount of solvent in the demulsifier composition is about 49% by weight. In some embodiments, the total amount of solvent in the demulsifier composition is about 50% by weight. In some embodiments, the total amount of solvent in the demulsifier composition is about 52% by weight.

[0061] In some embodiments, the demulsifier composition contains one or more clarifying agents. Examples of suitable clarifying agents include, but are not limited to, trimethylbenzene, naphthalene, and combinations thereof. In some embodiments, the clarifying agent is trimethylbenzene. In some embodiments, the clarifying agent is 1,2,4-trimethylbenzene. In some embodiments, the clarifying agent is naphthalene. In some embodiments, the clarifying agent is a mixture of 1,2,4-trimethylbenzene and naphthalene.

[0062] In some embodiments, the amount of clarifying agent in the demulsifier composition is from about 0.1 wt.% to about 10 wt.%, e.g., from about 0.1 wt.% to about 9 wt.%, from about 0.1 wt.% to about 8 wt.%, from about 0.1 wt.% to about 7 wt.%, from about 0.1 wt.% to about 6 wt.%, from about 0.1 wt.% to about 5 wt.%, from about 0.1 wt.% to about 4 wt.%, from about 0.1 wt.% to about 3 wt.%, from about 0.1 wt.% to about 2 wt.%, from about 0.1 wt.% to about 1 wt.%, from about 0.1 wt.% to about 0.5 wt.%, from about 0.5 wt.% to about 10 wt.%, from about 0.5 wt.% to about 9 wt.%, from about 0.5 wt.% to about 8 wt.%, from about 0.5 wt.% to about 7 wt.% Weight%, about 0.5% to about 6%, about 0.5% to about 5%, about 0.5% to about 4%, about 0.5% to about 3%, about 0.5% to about 2%, about 0.5% to about 1%, about 1% to about 10%, about 1% to about 9%, about 1% to about 1% by weight 8% by weight, about 1% to about 7%, about 1% to about 6%, about 1% to about 5%, about 1% to about 4%, about 1% to about 3%, about 1% to about 2%, about 2% to about 10%, about 2% to about 9%, about 2% to about 8%, about 2% to about 7% by weight, about 2% to about 6% by weight, about 2% to about 5% by weight, about 2% to about 4% by weight, about 2% to about 3% by weight, about 3% to about 10% by weight, about 3% to about 9% by weight, about 3% to about 8% by weight, about 3% to about 7% by weight, about 3% to about 6% by weight, about 3% by weight About 5% by weight, about 3% to about 4% by weight, about 4% to about 10% by weight, about 4% to about 9% by weight, about 4% to about 8% by weight, about 4% to about 7% by weight, about 4% to about 6% by weight, about 4% to about 5% by weight, about 5% to about 10% by weight, about 5% to about 9% by weight, about 5% by weight about 8% by weight, about 5% by weight to about 7% by weight, about 5% by weight to about 6% by weight, about 6% by weight to about 10% by weight, about 6% by weight to about 9% by weight, about 6% by weight to about 8% by weight, about 6% by weight to about 7% by weight, about 7% by weight to about 10% by weight, about 7% by weight to about 9% by weight, about 7% by weight to about 8% by weight, about 8% by weight to about 10% by weight, about 8% by weight to about 9% by weight, about 9% by weight to about 10% by weight, or about 0.1% by weight, about 0.5% by weight, about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, or about 10% by weight.In some embodiments, the amount of clarifying agent in the demulsifier composition is about 5% to about 10% by weight. In some embodiments, the amount of clarifying agent in the demulsifier composition is about 0.1% to about 5% by weight. In some embodiments, the amount of clarifying agent in the demulsifier composition is about 10% by weight. In some embodiments, the clarifying agent is 1,2,4-trimethylbenzene.

[0063] In some embodiments, the demulsifier composition of the present disclosure further contains one or more other solvents in addition to the solvent of the present disclosure. In some embodiments, the composition contains one or more additional solvents to increase the response of the emulsifier (less lag time). In some embodiments, the one or more additional solvents are selected from alcohols, alkylene glycols, and combinations thereof. In some embodiments, the one or more additional solvents include methanol, diethylene glycol, or combinations thereof. In some embodiments, the demulsifier composition of the present disclosure contains caprylic acid, methanol, and diethylene glycol.

[0064] Thus, the present disclosure provides a demulsifier composition comprising a demulsifying polymer as described herein and a solvent. In some embodiments, the solvent has an alkyl chain of 1 to 8 carbon atoms, a pKa of about 2 to about 7, a K of greater than about 0.1, ow , an alkyl carboxylic acid having a melting point of about 15° C. or less and a boiling point of about 80° C. or more. In some embodiments, the demulsifier composition contains a clarifier.

[0065] Also provided herein is a demulsifier composition comprising a demulsifying polymer as described herein and a solvent. In some embodiments, the solvent has an alkyl chain of 1 to 8 carbon atoms, a pKa of about 3 to about 6, a K of greater than about 0.1, ow , an alkyl carboxylic acid having a melting point of about 15° C. or less and a boiling point of about 80° C. or more. In some embodiments, the demulsifier composition contains a clarifier.

[0066] Also provided herein is a demulsifier composition comprising a demulsifying polymer as described herein and a solvent. In some embodiments, the solvent has an alkyl chain of 1 to 8 carbon atoms, a pKa of about 3 to about 6, a K of greater than about 0.1, ow , an alkyl carboxylic acid having a melting point below about 10°C and a boiling point above about 90°C.

[0067] In some embodiments, the demulsifier composition contains about 25% to about 50% by weight of the demulsifying polymer, about 20% to about 60% by weight of the solvent described herein, and about 0.1% to about 10% by weight of a clarifying agent. In some embodiments, the demulsifier composition contains about 35% to about 45% by weight of the demulsifying polymer, about 45% to about 55% by weight of the solvent described herein, and about 10% to about 15% by weight of a clarifying agent.

[0068] Methods of using demulsifier compositions containing demulsifying polymers The demulsifier compositions of the present disclosure, containing a demulsifying polymer and a solvent that is an alkyl carboxylic acid having an alkyl chain of 1 to 8 carbon atoms and a carboxylic acid functionality, have higher activity for dehydrating wet crude oil emulsions than known demulsifier compositions, such as those containing other solvents commonly found in demulsifier compositions, such as alcohols, alcohol ethers, and naphtha (aromatic, long chain and cyclic alkanes, as well as heavy hydrocarbons). Surprisingly, it has been found that the solvents of the present disclosure, in combination with the demulsifying polymer, significantly increase the water separation activity of the demulsifier compositions of the present disclosure. In some embodiments, the demulsifier compositions of the present disclosure are more effective at separating water from water-in-oil emulsions than known demulsifier compositions, including those that showed little or no effect on water separation in the same emulsions. In some embodiments, the demulsifier compositions of the present disclosure are used in water-in-oil emulsions in subterranean formations for drilling operations. In some embodiments, the demulsifier compositions of the present disclosure are used in oil field production in gas-oil separation plants. In some embodiments, the demulsifier compositions of the present disclosure are used for desalting in oil refineries. Accordingly, the present disclosure provides methods of using the solvent-containing demulsifier compositions of the present disclosure for such applications.

[0069] In some embodiments of the method, the demulsifier composition containing the demulsifying polymer and solvent of the present disclosure results in more than about 10 mL of water being separated after about 60 minutes at 50 ppm and 30° C., e.g., about 11 mL, about 12 mL, about 13 mL, about 14 mL, about 15 mL, about 16 mL, about 17 mL, about 18 mL, about 19 mL, about 20 mL, about 21 mL, about 22 mL, about 23 mL, about 24 mL, about 25 mL, or more. In some embodiments, a demulsifier composition comprising a demulsifying polymer and a solvent of the present disclosure removes at least about 35% by volume of water from a water-in-oil emulsion after about 60 minutes at 50 ppm and 30° C., e.g., at least about 40% by volume, about 45% by volume, about 50% by volume, about 55% by volume, about 60% by volume, about 65% by volume, about 70% by volume, about 75% by volume, about 80% by volume, about 85% by volume, about 90% by volume, about 95% by volume, or more. In some embodiments, the volume of water separated from a water-in-oil emulsion using the demulsifier composition of the present disclosure is at least about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 100%, or more of the volume of water separated from a water-in-oil emulsion using known demulsifier compositions that contain a solvent other than the solvent of the present disclosure.

[0070] In some embodiments, the demulsifier composition of the present disclosure is used to break down emulsions encountered in crude oil production. In some embodiments, the demulsifier composition of the present disclosure is introduced into the crude oil emulsion by injection before it enters the GOSP, by injection into the crude oil before desalting, or by injection into the crude oil process stream at a point between oil production and the final oil storage tank. The demulsifier composition can be injected continuously or in a batch mode. In some embodiments, injection is accomplished using an electric pump or a gas pump.

[0071] After injection, in some embodiments, the treated crude oil emulsion is left at rest until the desired separation into separate layers of water and oil has occurred. Once separation into separate layers of water and oil has occurred, any means known to those skilled in the art can be utilized to remove the free water and separate the crude oil.

[0072] A method for dehydrating a water-in-oil emulsion is also provided in the present disclosure. In some embodiments, the method comprises adding a demulsifier composition comprising a demulsifying polymer and a solvent as described herein to a water-in-oil emulsion. In some embodiments, the method comprises separating the water from the emulsion. In some embodiments, the water-in-oil emulsion is a crude oil emulsion. In some embodiments, the crude oil emulsion is a refinery desalted emulsion. In some embodiments, the crude oil emulsion is a crude oil production emulsion.

[0073] The present disclosure also provides a method for treating produced petroleum containing emulsions. In some embodiments, the method includes contacting the produced petroleum containing emulsions with a demulsifier composition to reduce or eliminate the emulsions. In some embodiments, the demulsifier composition includes a demulsifying polymer and a solvent as described herein. EXAMPLES

[0074] Example 1 - Preparation of Demulsifier Formulation A series of demulsifier formulations were prepared containing an alkoxylated phenolic demulsifying polymer, a clarifying agent and a series of solvents.

[0075] The demulsified alkoxylated phenolic polymers used in the formulations contained a formaldehyde-phenolic backbone with an oleophilic polypropylene oxide (PPO) section and a hydrophilic polyethylene oxide (PEO) section. The PEO and PPO monomer repeats ranged from 3 to 6 with a center of 4 units ( 11H-NMR). The formaldehyde-phenol skeleton was composed of a phenol with a para-saturated hydrocarbon chain consisting of seven carbons forming a para-tertiary-alkyl moiety. The phenol skeleton was composed of 5-10 phenol units with a 7 unit at the center ( 1 The demulsified polymer had a number average molecular weight (Mn) of 4278 g / mol (determined by GPC and MALDI-TOF) and the structure: [ka] had the following characteristics:

[0076] The demulsified alkoxylated phenolic polymer was combined with a clarifying agent and a solvent in the amounts shown in Table 1. [Table 1]

[0077] The fining agent was 1,2,4-trimethylbenzene, but naphthalene or a combination of these compounds could also be used.

[0078] Example 2 - Emulsion Bottle Test Bottle tests were performed on emulsions made with Arabian medium crude oil. The size of the bottle test was 100 mL. The Arabian medium crude oil used in this study had an API gravity of 28.8° and consisted of 30 wt% saturated hydrocarbons, 34 wt% aromatics, 11 wt% resins (NSO), and 25 wt% asphaltenes. The wet crude oil emulsions are very stable up to high temperatures of 80 °C. The methodology of the bottle test was that described by Raynel et al. (Oil Gas Sci. Technol.-Rev. IFP Energies Nouvelles (2021) 76:19).

[0079] The water separation performance of various demulsifier formulations at 50 ppm and 30°C is shown in Figure 1. All known solvents (entries 1-6 in Table 1) resulted in approximately 10 mL of water separated after 60 minutes. The solvents of the present disclosure (entries 8-11 in Table 1) showed an increase in water separation performance with increasing carbon number. No water separation was observed with methanesulfonic acid (MeSO3H), while 22 mL of water separation was observed with caprylic acid. The water content of the emulsion was 30% water by volume. Caprylic acid removed 72% water by volume from the emulsion after 60 minutes.

[0080] The partition coefficients (K ow ) a linear regression can be drawn between them (the diagonal line in Figure 2).

[0081] No relationship was observed between the same alcohol series, but there appeared to be an upper limit to the amount of water that could be separated with the commercially available solvents (entries 1–6).

Claims

1. About 25% to about 45% by weight of a demulsifying polymer; and about 30% to about 60% by weight of a solvent having an alkyl chain of 1 to 8 carbon atoms, a pKa of about 2 to about 7, and a K greater than about 0.1 ｏｗ a solvent, which is an alkyl carboxylic acid having the formula Demulsifier composition.

2. the demulsifying polymer is an alkoxylated phenolic polymer or an alkoxylated polyalcohol; The demulsifier composition of claim 1 .

3. the alkoxylated phenolic polymer is para-substituted with a saturated hydrocarbon chain; The demulsifier composition of claim 2.

4. the saturated hydrocarbon chain is selected from para-tertiary-alkyl, para-secondary-alkyl, para-iso-alkyl, para-cycloalkyl, and para-n-alkyl; The demulsifier composition of claim 3.

5. the saturated hydrocarbon chain is selected from para-tertiary-butylphenol, para-tertiary-amylphenol, para-tertiary-hexylphenol and para-tertiary-heptylphenol; The demulsifier composition of claim 3.

6. The alkoxylated phenolic polymer has the structure: 【Chemistry 1】 It has During the ceremony, R is a saturated hydrocarbon chain having 1 to 8 carbons; R′ and R″ are each independently H and C １ -C ２ alkyl; wherein the total number of carbon atoms in R, R', and R'' is 3 to 8; PPO has the formula: 【Chemistry 2】 is a polypropylene oxide having the formula: PEO has the formula: 【Transformation 3】 is a polyethylene oxide having the formula: x is an integer from 0 to 10; y is an integer from 0 to 10; and n is an integer from 3 to 10; The demulsifier composition of claim 2.

7. 10. The demulsifying polymer of claim 1, wherein the demulsifying polymer has the structure: 【Chemistry 4】 having The demulsifier composition of claim 6.

8. 10. The demulsifying polymer of claim 1, wherein the demulsifying polymer has the structure: 【Transformation 5】 having The demulsifier composition of claim 1 .

9. the demulsifier composition comprising about 30% to about 40% by weight of a demulsifying polymer; The demulsifier composition of claim 1 .

10. the demulsifier composition comprises about 45% to about 55% by weight of a solvent; The demulsifier composition of claim 1 .

11. The alkyl chain of the alkyl carboxylic acid is a straight chain or a branched chain. The demulsifier composition of claim 1 .

12. the pKa of the solvent is from about 3 to about 6; The demulsifier composition of claim 1 .

13. the alkyl carboxylic acid has a melting point of about 15°C or less; The demulsifier composition of claim 1 .

14. the alkyl carboxylic acid has a melting point of about 10°C or less; The demulsifier composition of claim 1 .

15. The alkyl carboxylic acid has a boiling point of about 80°C or higher. The demulsifier composition of claim 1 .

16. The alkyl carboxylic acid has a boiling point of about 90°C or higher. The demulsifier composition of claim 1 .

17. The solvent may have an alkyl chain of 1 to 8 carbon atoms, a pKa of about 2 to about 7, a K ｏｗ , an alkyl carboxylic acid having a melting point of about 15°C or less and a boiling point of about 80°C or more; The demulsifier composition of claim 1 .

18. The solvent may have an alkyl chain of 1 to 8 carbon atoms, a pKa of about 3 to about 6, a K ｏｗ , an alkyl carboxylic acid having a melting point of about 10°C or less and a boiling point of about 90°C or more; The demulsifier composition of claim 1 .

19. further comprising a fining agent, The demulsifier composition of claim 1 .

20. the fining agent is selected from 1,2,4-trimethylbenzene, naphthalene, and combinations thereof; 20. The demulsifier composition of claim 19.

21. the clarifying agent comprising from about 0.1% to about 10% by weight of the demulsifier composition; 20. The demulsifier composition of claim 19.

22. 10. A method for separating water from a water-in-oil emulsion, comprising adding the demulsifier composition of claim 1 to the emulsion and separating water from the emulsion. Method for dehydrating water-in-oil emulsions.

23. The water-in-oil emulsion is a crude oil emulsion.

23. The method of claim 22.

24. The crude oil emulsion is a refinery desalted emulsion.

24. The method of claim 23.

25. The crude oil emulsion is a crude oil production emulsion.

24. The method of claim 23.

26. 1. A method for treating produced petroleum containing emulsions, comprising: contacting the produced petroleum containing the emulsion with the demulsifier composition of claim 1 to reduce or eliminate the emulsion. method.

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