Asphaltene and paraffin dispersant compositions and uses thereof

Abstract

The present disclosure relates to methods and compositions for reducing contamination from natural and synthetic contaminants that tend to precipitate during the gathering, processing, transportation, and storage of hydrocarbons. The method includes applying a composition to a hydrocarbon containing contaminants. The composition includes an effective amount of the reaction product of an α-olefin / maleic anhydride copolymer and an amino-hydroxy compound. The contaminants may include, for example, waxes and asphaltenes.

Description

[Technical field]

[0001] The present disclosure relates generally to compositions and methods for dispersing pollutants. More specifically, the present disclosure provides dispersant compositions, such as asphaltene dispersant compositions and wax dispersant compositions, and methods of using such compositions for treating hydrocarbons. [Background technology]

[0002] Hydrocarbon processing plants, from refineries to petrochemical plants, suffer from fouling as a result of the deposition of hydrocarbon by-products that build up in heat exchangers, furnaces, water recycle loops, distillation columns, vessels, lines, overheads and other processing equipment. These by-products include various hydrocarbons that may be present in the crude oil, as well as by-products of the hydrocarbon refining process. Fouling of the internal surfaces of processing equipment occurs over a period that may vary from months to years depending on the unit considered.

[0003] Asphaltene deposition is a common fouling mechanism observed in refinery heat exchanger networks. Asphaltene occurs naturally in crude oil. Oil and petroleum fractions in transportation, refinery separation and other processing operations often contain asphaltene. Asphaltene is broadly defined as a solubility class of polydisperse high molecular weight hydrocarbons that are insoluble in non-polar solvents. Asphaltene is soluble in liquids with a surface tension of 25 dynes / cm or more, such as pyridine, carbon disulfide, carbon tetrachloride and benzene, and is insoluble in non-polar liquids with low surface tension, such as low boiling petroleum naphtha, petroleum ether, liquefied petroleum gas (e.g., methane, ethane, propane), pentane, isopentane, hexane, etc.

[0004] Asphaltene particles are believed to exist in the form of colloidal dispersions stabilized by other components of the crude oil. These naturally occurring dispersions can be destabilized by the various mechanical, thermal, and chemical conditions involved in petroleum production and processing. Blending of incompatible crude oils can also destabilize the asphaltenes. This destabilization can cause asphaltenes to aggregate, precipitate, and ultimately deposit tar-like residues on processing equipment. Summary of the Invention [Problem to be solved by the invention]

[0005] Asphaltenes are a widely recognized problem in hydrocarbon processing and are known to cause problems in various types of equipment where these compounds come into contact with internal surfaces. Unless dissolved and / or effectively dispersed, asphaltenes and other contaminants can accumulate and precipitate on any surface or surfaces they come into contact with within processing equipment or storage vessels, thereby causing fouling.

[0006] In addition to asphaltenes, hydrocarbons such as crude oil may also contain waxes. Such crude oils tend to leave residues and solids (known as "remains on board") on the walls of storage and transport vessels such as rail cars. Excessive residues reduce the efficiency of transporting the crude oil and increase costs associated with additional downtime for vessel cleaning as well as disposal of the residues removed from the vessel, thereby increasing the environmental burden. Vessels can be cleaned to remove the residues / solids, but this process generates hazardous waste, renders the vessel unusable during the cleaning period, and is expensive. [Means for solving the problem]

[0007] In some embodiments, the present disclosure provides a method for dispersing contaminants in a hydrocarbon. The method may include adding a composition to the hydrocarbon and dispersing the contaminants, the composition comprising an effective amount of a reaction product of an α-olefin / maleic anhydride copolymer and an amino-hydroxy compound. In some embodiments, the reaction product comprises a structure of formula I: [ka] In the formula, R is C8-C 36 It is an alkyl group, n is about 5 to about 200, and X is a linking group.

[0008] In some embodiments, X is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2(CH3)-, -CH2(CH3)CH2-, -CH2CH2NHCH2CH2-, or -CH2CH2OCH2CH2-.

[0009] In certain embodiments, the amino-hydroxy compound is a cyclic aliphatic compound, an acyclic aliphatic compound, or an aromatic compound.

[0010] In some embodiments, the cycloaliphatic compound is [ka] [ka] or [ka] is selected from.

[0011] In some embodiments, the acyclic aliphatic compound is [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] is selected from.

[0012] In some embodiments, the aromatic compound is [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] is selected from.

[0013] In certain embodiments, the contaminants include asphaltenes and / or waxes. In some embodiments, the composition is added continuously or intermittently to a hydrocarbon. In certain embodiments, the hydrocarbon includes crude oil.

[0014] In some embodiments, an effective amount of the reaction product is from about 1 ppm to about 10,000 ppm based on the volume of the hydrocarbon. In some embodiments, the composition comprises from about 1% to about 100% by weight of the reaction product. In some embodiments, the reaction product comprises a weight average molecular weight of from about 1,000 Da to about 100,000 Da.

[0015] In certain embodiments, the composition comprises a solvent selected from toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, ethylene glycol, ethylene glycol monobutyl ether, kerosene, propylene carbonate, glycol ethers, and any combination thereof.

[0016] In some embodiments, the composition excludes alkylphenols and / or alkylphenol alkoxylates or does not add alkylphenols and / or alkylphenol alkoxylates to the hydrocarbon.

[0017] The present disclosure also provides a dispersant comprising a hydrocarbon, a reaction product of an α-olefin / maleic anhydride copolymer and an amino-hydroxy compound, a solvent, and a contaminant. In certain embodiments, the dispersant comprises from about 1 ppm to about 10,000 ppm of the reaction product and from about 1 ppm to about 10,000 ppm of the solvent. In certain embodiments, the α-olefin is branched or linear.

[0018] In some embodiments, the reaction product comprises a structure of formula I: [ka] In the formula, R is C8-C 36is an alkyl group, n is 5 to 200, and X is a linking group. In some embodiments, X is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2(CH3)-, -CH2(CH3)CH2-, -CH2CH2NHCH2CH2-, or -CH2CH2OCH2CH2-.

[0019] In certain embodiments, the amino-hydroxy compound is any of the cyclic aliphatic, acyclic aliphatic, or aromatic compounds disclosed or contemplated by this disclosure.

[0020] In some embodiments, the dispersant is stable at temperatures from about 20° C. to about 400° C. In some embodiments, a hydrocarbon processing apparatus includes the dispersant. In some embodiments, the hydrocarbon includes crude oil. In some embodiments, the reaction product includes a weight average molecular weight of from about 1,000 Da to about 100,000 Da.

[0021] In certain embodiments, the composition comprises a solvent selected from toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, ethylene glycol, ethylene glycol monobutyl ether, kerosene, propylene carbonate, glycol ethers, and any combination thereof.

[0022] In some embodiments, the dispersant excludes alkylphenols and / or alkylphenol alkoxylates. In some embodiments, the reaction product does not include acid groups and / or the dispersant does not include compounds with acid groups.

[0023] The foregoing has outlined rather broadly the features and technical advantages of the present disclosure so that the detailed description of the embodiments that follow may be better understood. Additional features and advantages of the present disclosure will be described hereinafter which form the subject of the claims of this application. It should be appreciated by those skilled in the art that the conception and specific embodiments disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present disclosure. It should also be appreciated by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the present disclosure as set forth in the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The present disclosure provides compositions and methods for treating contaminants contained in hydrocarbons, such as crude oil. The methods and compositions reduce contamination by natural and synthetic contaminants that tend to precipitate during collection, processing, transportation, and storage of the hydrocarbons. The methods include applying a composition to the hydrocarbons, where the composition helps reduce contamination and form a stable dispersion over a wide range of processing conditions. The compositions and methods disclosed herein are useful for inhibiting precipitation and / or deposition of contaminants.

[0025] As used herein, the term "contaminant" refers to any species or species that are present in and can precipitate from a hydrocarbon. Contaminants include natural contaminants, synthetic contaminants, or a combination thereof. "Natural contaminants" refers to any contaminant species that are inherently present in crude oil. For example, natural contaminants may include asphaltenes, waxes, heavy oils, tars, and aliphatic and aromatic hydrocarbons that have a density lower than that of water. "Synthetic contaminants" are contaminant species that are by-products of the hydrocarbon refining process. Synthetic contaminants may include, for example, polynuclear aromatic hydrocarbons, coke, oxygenated hydrocarbons, polymers formed from the polymerization of vinyl by-products of hydrocarbon processing such as styrene, butadiene, cyclopentadiene, and pyrolysis products resulting from the cracking of larger molecules.

[0026] As used herein, the terms "hydrocarbon process equipment," "hydrocarbon process apparatus," and like terms refer to articles having an internal surface, such as a surface comprising metal, with one or more hydrocarbon products in fluid contact with the surface for any time and at any temperature. Hydrocarbon process equipment includes articles for removing hydrocarbon products from an underground reservoir, for transporting one or more hydrocarbon products from a first location to a second location, or for separating, purifying, treating, isolating, distilling, reacting, metering, heating, cooling, or containing one or more hydrocarbon products.

[0027] It has been discovered that natural and / or synthetic contaminants, such as asphaltenes, present in hydrocarbon process streams can be dispersed using a composition comprising, consisting essentially of, or consisting of an effective amount of the reaction product of an α-olefin / maleic anhydride copolymer and an amino-hydroxy compound.

[0028] The compositions disclosed herein have also been found to be effective in reducing wax deposits in crude oil storage and transport vessels. Without being bound to any particular theory, it is believed that the compositions disclosed herein disperse wax, dissolve wax, and / or provide wax slippage on metal surfaces in contact with certain crude oils. These compositions may also inhibit the adhesion of wax deposits on surfaces such as metal surfaces.

[0029] α-Olefin / Maleic Anhydride Copolymer is C8~C 36 In some embodiments, the α-olefin is a copolymer of an α-olefin and maleic anhydride. 10 ~C 36 Alkyl group, C 12 ~C 36 Alkyl group, C 14 ~C 36 Alkyl group, C 16 ~C 36 Alkyl group, C 18 ~C36 Alkyl group, C 20 ~C 36 Alkyl group, C 22 ~C 36 Alkyl group, C 24 ~C 36 Alkyl group, C 26 ~C 36 Alkyl group, C 28 ~C 36 Alkyl group, C 30 ~C 36 Alkyl group, C 32 ~C 36 Alkyl group or C 34 ~C 36 It is an alkyl group.

[0030] The alkyl group may be substituted or unsubstituted, straight chain and / or branched chain.

[0031] The α-olefin / maleic anhydride copolymer is reacted with an amino-hydroxy compound to form the contaminant dispersant disclosed herein. The amino-hydroxy compound is not particularly limited and may be selected from any compound that contains both amino and hydroxyl groups.

[0032] In some embodiments, the amino-hydroxy compound is an aliphatic or cycloaliphatic compound. For example, the amino-hydroxy compound is [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] You may choose from.

[0033] In some embodiments, the amino-hydroxy compound is an aromatic amino-hydroxy compound. For example, the amino-hydroxy compound is [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] You may choose from.

[0034] In some embodiments, the reaction product of the α-olefin / maleic anhydride copolymer and an amino-hydroxy compound comprises a structure selected from Formula 1: [ka] In the formula, R is C8-C 36 is an alkyl group, X is a linking group, and n is selected from about 5 to about 200. In some embodiments, n is selected from 5 to 150, 5 to 100, 5 to 75, 5 to 50, 10 to 50, 10 to 75, 10 to 100, 10 to 150, or 10 to 200. In some embodiments, R is C 10 ~C 36 Alkyl group, C 12 ~C 36 Alkyl group, C 14 ~C 36 Alkyl group, C 16 ~C 36 Alkyl group, C 18 ~C 36 Alkyl group, C 20 ~C 36 Alkyl group, C 22 ~C 36 Alkyl group, C 24 ~C 36 Alkyl group, C 26 ~C 36 Alkyl group, C 28 ~C 36 Alkyl group, C 30 ~C 36 Alkyl group, C 32 ~C 36 Alkyl group or C 34 ~C 36 Alkyl groups. Alkyl groups may be substituted or unsubstituted, straight chain and / or branched chain.

[0035] Illustrative non-limiting examples of linking groups include alkylene and arylene groups. Illustrative non-limiting examples of linking groups include -CH-, -CHCH-, -CHCHCH-, CHCH(CH)-, -CH(CH)CH-, -CHCHNHCHCH-, and -CHCHOCHCH-.

[0036] Unless otherwise indicated, the alkyl groups described herein alone or as part of another group are optionally substituted straight or branched chain saturated monovalent hydrocarbon substituents containing, for example, from 1 to about 36 carbon atoms in the main chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, and the like.

[0037] As used herein, the terms "aryl" or "ar" used alone or as part of another group (e.g., arylene) refer to optionally substituted homocyclic aromatic groups such as monocyclic or bicyclic groups containing from about 6 to about 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl, etc. The term "aryl" also includes heteroaryl.

[0038] The term "substituted" as in "substituted alkyl" means that in the group (i.e., the alkyl group), at least one hydrogen atom bonded to a carbon atom is substituted with a hydroxy (-OH), alkylthio, phosphino, amido (-CON(R A )(R B )(wherein, R A and R B are independently hydrogen, alkyl, or aryl), amino (-N(R A )(R B )(wherein, R A and R B are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (-NO2), ether (-OR A (In the formula, R A is alkyl or aryl), esters (-OC(O)R A (In the formula, R A is alkyl or aryl), keto (-C(O)R A (In the formula, R Ameans substituted with one or more substituents, such as alkyl or aryl), heterocyclo, etc.

[0039] Where the term "substituted" introduces a list of possible substituents, it is intended that the term apply to every member of that group, i.e., the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optionally substituted aryl."

[0040] The weight average molecular weight of the reaction product of the α-olefin / maleic anhydride copolymer and the amino-hydroxy compound is not particularly limited. In some embodiments, the reaction product comprises a weight average molecular weight of about 1,000 Da to about 100,000 Da.

[0041] For example, the reaction product of an α-olefin / maleic anhydride copolymer with an amino-hydroxy compound may have a molecular weight of about 1,000 Da to about 80,000 Da, about 1,000 Da to about 60,000 Da, about 1,000 Da to about 40,000 Da, about 1,000 Da to about 20,000 Da, about 5,000 Da to about 80,000 Da, about 5,000 Da to about 60,000 Da, about 5,000 Da to about 40,000 Da. , about 5,000 Da to about 20,000 Da, about 10,000 Da to about 80,000 Da, about 10,000 Da to about 60,000 Da, about 10,000 Da to about 40,000 Da, about 20,000 Da to about 80,000 Da, about 20,000 Da to about 60,000 Da, about 20,000 Da to about 40,000 Da, or about 30,000 Da to about 50,000 Da.

[0042] Amino-hydroxy compounds are bifunctional compounds and may react with anhydrides through both amino and hydroxy functional groups. Amine groups are more nucleophilic than hydroxyl groups, have higher reactivity, and react with anhydrides under milder conditions compared to hydroxy groups. Three possible ring-opening products may be obtained from the reaction of amino-hydroxy compounds with anhydrides. Illustrative, non-limiting examples are shown below. However, the amino-hydroxy compounds are not limited to the following, and any amino-hydroxy compounds may be used. [ka]

[0043] As can be seen, the reaction produces a half-amide-half-acid structure. [ka] , half amide-half ester structure [ka] , and / or half acid-half ester structure [ka] ) may be generated.

[0044] In certain embodiments, the reaction products of the present disclosure include or exclude half amide-half acid structures. In certain embodiments, the reaction products include or exclude half amide-half ester structures. In certain embodiments, the reaction products include or exclude half acid-half ester structures.

[0045] According to certain embodiments of the present disclosure, the composition may include a solvent, which may be selected from, for example, toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, kerosene, propylene carbonate, paraffinic solvents, and any combination thereof.

[0046] In some embodiments, the alcohol may be selected from methanol, ethanol, isopropanol, 2-ethylhexanol, benzyl alcohol, and any combination thereof. In some embodiments, the glycol may be ethylene glycol or a glycol ether, such as ethylene glycol monobutyl ether.

[0047] The compositions disclosed herein may include or exclude other additives, for example, corrosion inhibitors, viscosity reducers, friction reducers, scale inhibitors, clay swelling inhibitors, biocides, additional asphaltene dispersants, additional wax dispersants, backflow aids, emulsifiers, demulsifiers, hydrogen sulfide scavengers, hydrate inhibitors, pH adjusters, surfactants, and / or other chemical processing additives used in crude oil production, refining, and chemical processing.

[0048] In some embodiments, the compositions of the present disclosure may include 0 to about 50% by weight of one or more additives, based on the total weight of the composition. For example, the compositions may include from about 0.01% to about 50% by weight, from about 0.01% to about 40% by weight, from about 0.01% to about 30% by weight, from about 0.01% to about 20% by weight, from about 0.01% to about 10% by weight, from about 0.01% to about 5% by weight, from about 0.01% to about 1% by weight, from about 0.1% to about 50% by weight, from about 0.1% to about 40% by weight, from about 0.1% to about 30% by weight, from about 0.1% to about 20% by weight, from about 0.1% to about 10% by weight, from about 0.1% to about 5% by weight, from about 0.1% to about 1% by weight, from about 0.0 ...01% to about 50% by weight, from about 0.01% to about 50% by weight, from about 0.01% to about 50% by weight, from about 0.01% to about 50% by weight, from about 0.01% to about 50% by weight, from about 0.01% to about 50% by weight, from about 0.01% to 0.5% to about 50% by weight, about 0.5% to about 40% by weight, about 0.5% to about 30% by weight, about 0.5% to about 20% by weight, about 0.5% to about 10% by weight, about 0.5% to about 5% by weight, about 0.5% to about 1% by weight, about 1% to about 50% by weight, about 1% to about 40% by weight, about 1% to about 30% by weight, about 1% to about 20% by weight, about 1% to about 30% by weight, about 1% to about 20% by weight, about 1% to about 10% by weight, or about 1% to about 5% by weight of one or more additives.

[0049] In some embodiments, the compositions of the present disclosure include from about 1% to about 100% by weight of the reaction product of an α-olefin / maleic anhydride copolymer and an amino-hydroxy compound. For example, the composition may include from about 1% to about 90% by weight, from about 1% to about 80% by weight, from about 1% to about 70% by weight, from about 1% to about 60% by weight, from about 1% to about 50% by weight, from about 1% to about 40% by weight, from about 1% to about 30% by weight, from about 1% to about 20% by weight, from about 1% to about 10% by weight, from about 5% to about 10% by weight, from about 5% to about 20% by weight, from about 5% to about 30% by weight, from about 5% to about 40% by weight, from about 5% to about 50% by weight, from about 5% to about The reaction product may comprise about 60% by weight, about 5% to about 70% by weight, about 5% to about 80% by weight, about 5% to about 90% by weight, about 10% to about 90% by weight, about 10% to about 80% by weight, about 10% to about 70% by weight, about 10% to about 60% by weight, about 10% to about 50% by weight, about 10% to about 40% by weight, about 10% to about 30% by weight, about 20% to about 60% by weight, about 30% to about 60% by weight, or about 40% to about 60% by weight.

[0050] In some embodiments, the compositions disclosed herein exclude alkylphenol compounds and / or alkylphenol alkoxylates.

[0051] The contaminant dispersants disclosed herein are pyrolytically stable under conditions typically used or encountered in hydrocarbon process streams. Thus, the contaminant dispersants may be added to one or more hydrocarbon process streams prior to subjecting the process stream to one or more pyrolytically challenging processes, such as hydrotreating. The contaminant dispersants retain their antifouling properties during hydrocarbon processing at temperatures between about 20° C. and 400° C. Additionally, the contaminant dispersants are hydrolytically stable (not susceptible to hydrolysis) and therefore suitable for use in hydrocarbon process streams contaminated with water, such as about 1% by weight or less of water.

[0052] Also provided herein are stable dispersants, such as dispersants comprising the compositions of the present disclosure, including hydrocarbons, reaction products of the α-olefin / maleic anhydride copolymers disclosed herein with amino-hydroxy compounds, any solvents disclosed or contemplated by the present disclosure, and contaminants.

[0053] In some embodiments, the dispersant comprises from about 1 ppm to about 10,000 ppm of the reaction product. For example, the dispersant may comprise from about 1 ppm to about 8,000 ppm, from about 1 ppm to about 6,000 ppm, from about 1 ppm to about 4,000 ppm, from about 1 ppm to about 2,000 ppm, from about 1 ppm to about 1,000 ppm, from about 1 ppm to about 500 ppm, from about 1 ppm to about 250 ppm, from about 1 ppm to about 100 ppm, from about 100 ppm to about 8,000 ppm, from about 100 ppm to about 6,000 ppm, from about 100 ppm to about 4,000 ppm, or from about 100 ppm to about 5,000 ppm. The reaction product may comprise about 00 ppm, about 100 ppm to about 2,000 ppm, about 100 ppm to about 1,000 ppm, about 100 ppm to about 500 ppm, about 100 ppm to about 250 ppm, about 500 ppm to about 8,000 ppm, about 500 ppm to about 6,000 ppm, about 500 ppm to about 4,000 ppm, about 500 ppm to about 2,000 ppm, or about 500 ppm to about 1,000 ppm.

[0054] In some embodiments, the dispersant may contain from about 1 ppm to about 10,000 ppm of solvent. For example, the dispersant may contain from about 1 ppm to about 8,000 ppm, from about 1 ppm to about 6,000 ppm, from about 1 ppm to about 4,000 ppm, from about 1 ppm to about 2,000 ppm, from about 1 ppm to about 1,000 ppm, from about 1 ppm to about 500 ppm, from about 1 ppm to about 250 ppm, from about 1 ppm to about 100 ppm, from about 100 ppm to about 8,000 ppm, from about 100 ppm to about 6,000 ppm, from about 100 ppm to about 4,000 ppm, from about 1 ppm to about 5,000 ppm, from about 1 ppm to about 6,000 ppm, from about 100 ppm to about 8,000 ppm, from about 100 ppm to about 4,000 ppm, from about 1 ppm to about 5,000 ppm, from about 100 ppm to about 5,000 ppm, from about 100 ppm to about 5,000 ppm, from about 100 ppm to about 6,000 ppm, from about 100 ppm to about 7,000 ppm, from about 100 ppm to about 8,000 ppm, from about 100 ppm to about 9,000 ppm, from about 100 ppm to about 10 ... The solvent may be contained in an amount of about 1,000 ppm, about 100 ppm to about 2,000 ppm, about 100 ppm to about 1,000 ppm, about 100 ppm to about 500 ppm, about 100 ppm to about 250 ppm, about 500 ppm to about 8,000 ppm, about 500 ppm to about 6,000 ppm, about 500 ppm to about 4,000 ppm, about 500 ppm to about 2,000 ppm, or about 500 ppm to about 1,000 ppm.

[0055] The amount of contaminants in a dispersant depends on many factors, such as the type of hydrocarbon and the origin of the hydrocarbon. For example, crude oil typically contains about 10% to about 70% by weight of wax. Additionally, crude oil typically contains about 0% to about 50% by weight of asphaltenes.

[0056] The dispersants disclosed herein may be present and stable at temperatures ranging from about 20°C to about 400°C.

[0057] The present disclosure also provides a method for producing a pollutant dispersant, in some embodiments, the synthesis includes free radical polymerization of maleic anhydride with an α-olefin to produce an α-olefin maleic anhydride copolymer, and condensation of the copolymer with an amino alcohol to form a hydroxy-succinimide copolymer.

[0058] In an illustrative, non-limiting example, α-olefin / maleic anhydride copolymers (3) (OMAC) are synthesized by reacting α-olefins (1) with maleic anhydride (2) using conventional techniques, such as radical addition polymerization principles and techniques well known to those skilled in the art of polymer synthesis (Scheme 1). The synthesis of such precursor polymers is also described in U.S. Patent No. 5,214,224 to Corner et al., which is expressly incorporated by reference into this application. [ka]

[0059] The copolymer may, for example, comprise a molar ratio of α-olefin to maleic anhydride in the range of 1:5 to 5:1. The weight average molecular weight of the copolymer may, for example, be from about 5,000 Da to about 300,000 Da, such as about 100,000 Da, as analyzed by, for example, gel permeation chromatography (GPC).

[0060] The copolymer (3) is then reacted with an amino-hydroxy compound (4) to form a pollutant dispersant (5). [ka]

[0061] The reaction may be carried out at a temperature of about 100° C. to about 180° C. to provide a hydroxy-containing succinimide in the backbone via elimination of a water molecule. For example, the reaction may be carried out at a temperature of about 120° C. to about 180° C., about 140° C. to about 180° C., or about 160° C. to about 180° C.

[0062] The amino-hydroxy compound can be any compound that contains an amino group and a hydroxy group. For example, the amino-hydroxy compound can be any acyclic or cyclic aliphatic amino-hydroxy compound herein or any aromatic amino-hydroxy compound disclosed herein. The reaction can be carried out, for example, using a molar ratio of amine moiety to anhydride moiety of about 1:1. The reaction is carried out in a solvent such as a petroleum solvent (e.g., paraffinic solvent, mineral oil, "HAN" or heavy aromatic naphtha / Aromatic 150, any mixture thereof, etc.).

[0063] The present disclosure further provides a method for dispersing contaminants in a hydrocarbon. During the practice of the method, the compositions disclosed herein may be applied batchwise, continuously, or semi-continuously to a hydrocarbon process stream. In some embodiments, application of the composition is manual, while in other embodiments, application is automated. The amount of the composition applied over a selected time unit may vary.

[0064] In some embodiments, the hydrocarbons present in the one or more hydrocarbon process streams are crude oil, reduced crude oil, crude oil distillate, heavy oil, bitumen, coker charge, hydrotreater influent, flash crude oil, light cycle oil, or diesel or naphtha refinery streams. In some embodiments, the hydrocarbon process unit is any unit conventionally associated with the gathering, processing, transport, or storage of one or more crude oil, reduced crude oil, crude oil distillate, heavy oil, bitumen, coker charge, hydrotreater influent, flash crude oil, light cycle oil, or diesel or naphtha refinery streams, including piping and associated infrastructure used to fluidly connect the process unit items and together facilitate the processing of the process streams located therein.

[0065] The treated process stream may be a treated liquid hydrocarbon product placed in fluid contact with an internal surface of a hydrocarbon processing equipment, whereby contamination of the contacted internal surface is reduced or eliminated. In some embodiments, the treated process stream has between 50% and 100% reduced contamination compared to the corresponding process stream (i.e., the untreated process stream), or has between about 60% and 100%, or between about 70% and 100%, or between about 80% and 100%, or between about 90% and 100%, or between about 95% and 100% reduced measurable contamination of the internal surface of the hydrocarbon processing equipment compared to the corresponding process stream.

[0066] The contamination reduction rate may be determined, for example, by the following test: A selected volume of treated liquid hydrocarbon product is added to hexane or heptane to form a 1% to 100% solution of the hydrocarbon product, and the diluted product is allowed to stand at about 20°C for 2 hours. The precipitate formed is then measured volumetrically and reported as a percentage of the precipitate observed in a control sample, which is the corresponding untreated hydrocarbon product. Contamination may be measured as the relative increase in the retention of solids in the treated hydrocarbon product compared to the retention of solids in the untreated hydrocarbon product over the same period. Contamination may also be measured as the relative reduction in the weight or volume of precipitate resulting from a selected period of contact of the treated hydrocarbon treatment stream in the relevant hydrocarbon treatment equipment item compared to the same period of contact of the hydrocarbon treatment equipment with the corresponding untreated hydrocarbon treatment stream. Stated differently, the reduction in contamination is the relative reduction in the measured weight or volume of solids deposited or precipitated from a hydrocarbon treatment equipment contacted with a treated hydrocarbon treatment stream over a selected period of time when compared to the weight or volume of solids deposited or precipitated from the untreated hydrocarbon treatment stream over the same period of time.

[0067] In some embodiments, the treated hydrocarbon process stream (the stream to which the composition has been added) is placed in a hydrocarbon treatment device, the device comprising an interior surface, such as a surface comprising a metal, and the treated hydrocarbon stream is in fluid contact with the surface.

[0068] In some embodiments, the composition is introduced into the crude oil by injecting it below the surface of the well, by injecting it into the crude oil at the wellhead, or by injecting it into the crude oil processing stream at a point between the wellhead and the final oil storage tank. The composition may be injected, for example, in a continuous or batch mode. Injection is typically accomplished using electric or gas pumps.

[0069] Additionally, where the composition is to be applied as a wax dispersant, a method of reducing wax deposition may be implemented. The method may, for example, reduce wax deposition in a crude oil storage or transport vessel. The method may include adding the composition to the crude oil in an amount effective to reduce wax deposition in the storage or transport vessel containing the crude oil.

[0070] In some embodiments, the crude oil consists essentially of crude oil of any API gravity, such that it does not contain any significant amount or any quantity of refined hydrocarbon products such as distillates (e.g., cold flow distillates or diesel fuel).

[0071] The storage or transport vessel can be any vessel used to store or transport crude oil, including, but not limited to, a storage tank, a rail car, a tank truck, a ship, a barge, or a pipeline. In some embodiments, the composition can be added to crude oil contained in a storage tank, a rail car, or a tank truck.

[0072] The amount of contaminant dispersant added will depend on certain factors such as the particular hydrocarbon being treated. Generally, an effective amount of contaminant dispersant will range from about 1 ppm to about 10,000 ppm based on the volume of oil. For example, an effective amount may be from about 1 ppm to about 8,000 ppm, from about 1 ppm to about 6,000 ppm, from about 1 ppm to about 4,000 ppm, from about 1 ppm to about 2,000 ppm, from about 1 ppm to about 1,000 ppm, from about 1 ppm to about 500 ppm, from about 1 ppm to about 250 ppm, from about 1 ppm to about 100 ppm, or from about 1 ppm to about 50 ppm based on the volume of oil.

[0073] In some embodiments, when applied as an asphaltene dispersant, an effective amount may be from about 1 ppm to about 1,000 ppm, although the amounts described in the preceding paragraph may be used as well. In some embodiments, when applied as a wax dispersant, an effective amount may be from about 1 ppm to about 5,000 ppm, although the amounts described in the preceding paragraph may be used as well.

[0074] The above may be better understood by reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the disclosure or its application in any way. EXAMPLES

[0075] Working Example

[0076] Below is a representative synthesis scheme for polymer 1. [ka]

[0077] C, in which the molar ratio of amine moieties to anhydride moieties is about 1:1; 24 -C 28 Copolymers of α-olefins and maleic anhydride (CAS number 68459-79-0) were obtained following the procedure outlined in US Pat. No. 5,214,224.

[0078] The reagents and amounts used in the reaction are shown in Table 1. The molar ratio of maleic anhydride residues in the backbone to 3-aminophenol used in this reaction was approximately 1:1.

[0079] [Table 1]

[0080] A 250 mL, 4-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar was charged with C 24 ~C 28α-Olefin maleic anhydride copolymer (about 14.4 g) was added. The polymer was then diluted with about 82 g of HAN and the temperature was increased to about 65° C. 3-aminophenol was then added to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to increase to about 80° C. The resulting suspension was heated to about 160° C. under a nitrogen blanket and stirred for about 6 hours or until the reaction was complete. As the reaction proceeded to completion, the suspension turned into a homogenous product. The resulting product was characterized by NMR and IR techniques. No peaks associated with anhydride or imide groups were observed in the final product.

[0081] Using the general synthesis described above, C 24 ~C 28 Starting from α-olefin maleic anhydride copolymers and the corresponding amino-hydroxy compounds, the polymers listed in Table 2 were synthesized.

[0082] [Table 2]

[0083] Polymers 1, 2, 3, and 4 were screened for their effectiveness as asphaltene dispersants. In the tests, a volume of crude oil was dissolved in n-heptane or n-hexane, an environment that promotes asphaltene precipitation. The effectiveness of each asphaltene stabilizer was observed by comparing the volume of precipitate formed in each tube after 2 hours of static settling. More effective dispersants produced less precipitate volume.

[0084] The Asphaltene Dispersant Test (ADT) is widely used in the oil and gas industry to screen and evaluate "asphaltene dispersants". The procedure is used to compare the asphaltene content of crude oils and to evaluate the ability of asphaltene dispersants to disperse the asphaltene within such oils. The basis of the Asphaltene Dispersant Test is to determine the relative effectiveness of dispersants in keeping asphaltene dispersed in a non-solvent medium.

[0085] ADT exploits the insolubility of asphaltene in alkane diluents (e.g., paraffinic organic solvents such as heptane). When a fixed volume of asphaltenic material (such as crude oil) is diluted with a fixed amount of alkane diluent, the asphaltene precipitates. When the same fixed volume of asphaltenic material with an appropriate dose of dispersant is diluted in the same fixed volume of alkane diluent, the amount of asphaltene precipitation is minimized over a controlled test period.

[0086] An effective dispersant will prevent asphaltenes from flocculating and ultimately precipitating when the sample is diluted with an alkane diluent. Thus, the desired result is little or no precipitation of asphaltenic materials, and samples with the least accumulation (most dispersed) of these materials will show the best results. Precipitation measured by this procedure is predictive of relative fouling behavior in petroleum process streams.

[0087] The equipment used in the experiment included 10-15 mL graduated conical centrifuge tubes, a timer, and a light box and / or flashlight to facilitate viewing of sediments present in the dark petroleum liquid. The centrifuge tubes were filled with a predetermined volume of crude oil. The tubes were then filled with a specific amount of dispersant. One tube served as a blank and was left untreated. 10 mL of n-heptane was added to each centrifuge tube, and each tube was mixed thoroughly to ensure all of the oil was dispersed. Once all tubes were thoroughly mixed, the tubes were placed in a test tube rack in front of a bright light. After 2 hours of static settling, the relative volume of sediment in each tube was recorded.

[0088] In the first series of tests, polymers 1-3 were compared with two prior art dispersants. The ADT conditions were as follows: ●Crude oil A:20.3°API specific gravity ●Crude oil volume: 100μL Dispersant dosage: 10 ppm active material Paraffin-based solvent: 10 mL n-heptane ●Exam time: 2 hours

[0089] The data is shown below in Table 3, which shows the sediment volume.

[0090] [Table 3]

[0091] In a second series of tests, the asphaltene dispersant performance of polymers 1-3 and 5-7 was compared to two prior art dispersants. The ADT conditions were as follows: ● Crude oil tested: 36.1° API gravity ●Crude oil volume: 500μL Dispersant dosage: 5 ppm active material Paraffin-based solvent: n-heptane 10mL ●Exam time: 2 hours

[0092] The data is shown below in Table 4, which shows the sediment volumes.

[0093] [Table 4]

[0094] In the third test, the asphaltene dispersant performance of Polymer 4 was evaluated in three different crude oils. The ADT conditions were as follows: Tested crude oils: 19.2, 24.8, and 31.0° API crude oils ●Crude oil volume: 50~200μL Dispersant dosage: 10 ppm active material Paraffin-based solvent: n-heptane 10mL ●Exam time: 2 hours

[0095] The data is shown below in Table 5, which shows the sediment volume.

[0096] [Table 5]

[0097] The final test evaluated the wax dispersant properties. Crude and heavy oils are typically C 10 ~C 60 Oils contain long chain paraffins in the range of 0.1 to 1.0 mmHg. When the oil is cooled below the wax appearance temperature, the paraffins crystallize from the oil to form wax. The presence of wax increases the viscosity and pour point of the oil. This reduces the pumping rate and creates wax deposit problems when the oil is pumped through a pipeline. Pour point depressants / wax dispersants are materials used to reduce the pour point and viscosity of crude oil. These compounds interact with the paraffins in the oil to reduce the wax crystal size and prevent wax crystal agglomeration.

[0098] The ASTM D5950 pour point test is a method to evaluate the minimum temperature at which a crude oil will flow. The effectiveness of pour point depressants can also be evaluated. The pour point test was performed using a PAC Instruments OptiCPP. The oil was preheated to about 52°C before the test.

[0099] Vacuum gas oil was heated to about 52°C and condensed with 2-aminoethan-1-ol to produce 1,000 ppm of 49% by weight C. 24 ~C 28 The oil was treated with an α-olefin maleic anhydride copolymer. As can be seen from the data shown in Table 6, the polymers were able to reduce the pour point of the oil from 33° C. to 6° C., clearly demonstrating the effectiveness of these compounds as pour point depressants.

[0100] [Table 6]

[0101] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. The present invention may be embodied in many different forms, and certain preferred embodiments of the present invention are described in detail herein. The present disclosure is an exemplification of the principles of the present invention, and is not intended to limit the invention to the specific embodiments illustrated. It should be noted that unless expressly stated otherwise, the term "a" is intended to include "at least one" or "one or more." For example, "a dispersant" is intended to include "at least one dispersant" or "one or more dispersants."

[0102] Any ranges expressed in either absolute or approximate terms are intended to encompass both, and any definitions used herein are intended to be illustrative, not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein should be understood to encompass any and all subranges subsumed therein, including all fractional and whole values.

[0103] Any composition disclosed herein can comprise, consist of, or consist essentially of any element, component, and / or ingredient disclosed herein, or any combination of two or more of the elements, components, or ingredients disclosed herein.

[0104] Any method disclosed herein may comprise, consist of, or consist essentially of any method step(s) disclosed herein, or any combination of two or more of the method steps disclosed herein.

[0105] The transitional phrase "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements, components, ingredients, and / or method steps.

[0106] The transitional phrase "consisting of" excludes any element, component, ingredient, and / or method step not specified in the claim.

[0107] The transitional phrase "consisting essentially of" limits the scope of the claim to certain elements, components, ingredients, and / or steps, and those that do not materially affect the basic and novel characteristics of the claimed invention.

[0108] Unless otherwise specified, all molecular weights referred to herein are weight average molecular weights and all viscosities were measured at 25° C. using neat (undiluted) polymer.

[0109] As used herein, the term "about" refers to a cited value that is within error resulting from the standard deviation found in their respective testing measurements; where such error cannot be determined, "about" may refer, for example, to within 5% of the cited value.

[0110] Moreover, the present invention encompasses all possible combinations of any or all of the various embodiments described herein. It should also be understood that various changes and modifications to the preferred embodiments of the present invention described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its intended advantages. Accordingly, such changes and modifications are intended to be covered by the appended claims.

Claims

1. 1. A method for dispersing contaminants in a hydrocarbon, comprising the steps of: adding a composition to the hydrocarbon, the composition comprising an effective amount of the reaction product of an α-olefin / maleic anhydride copolymer and an amino-hydroxy compound; dispersing the contaminant. How to disperse.

2. The reaction product has formula I: 【Chemistry 1】 wherein R is C ８ ~C ３６ is an alkyl group, n is from about 5 to about 200, and X is a linking group; The method of claim 1.

3. The method of claim 1 or 2, wherein the amino-hydroxy compound is a cyclic aliphatic compound, an acyclic aliphatic compound, or an aromatic compound.

4. The cyclic aliphatic compound is 【Chemistry 2】 【Chemistry 3】 The method of claim 3, wherein the compound is selected from the group consisting of

5. The acyclic aliphatic compound is 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 The method of claim 3, wherein the compound is selected from the group consisting of

6. The aromatic compound is 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 【Chemistry 18】 【Chemistry 19】 【Chemistry 20】 The method of claim 3, wherein the compound is selected from the group consisting of

7. The method of claim 1 or 2, wherein the contaminants include asphaltenes and / or waxes.

8. 3. The method of claim 1 or 2, wherein the composition is added to the hydrocarbon continuously or intermittently.

9. The method of claim 1 or 2, wherein the hydrocarbon comprises crude oil.

10. 3. The method of claim 1 or 2, wherein the effective amount of reaction product is from about 1 ppm to about 10,000 ppm based on the volume of the hydrocarbon.

11. The method of claim 1 or 2, wherein the composition comprises from about 1% to about 100% by weight of the reaction product.

12. 3. The method of claim 1 or 2, wherein the reaction product comprises a weight average molecular weight of about 1,000 Da to about 100,000 Da.

13. X is an alkylene group, an arylene group, -CH ２ CH ２ N.H.C.H. ２ CH ２ -or-CH ２ CH ２ OCH ２ CH ２ The method according to claim 2, wherein

14. 3. The method of claim 1 or 2, wherein the composition comprises a solvent selected from the group consisting of toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, ethylene glycol, ethylene glycol monobutyl ether, kerosene, propylene carbonate, glycol ethers, and any combination thereof.

15. 3. The method of claim 1 or 2, wherein the composition excludes alkylphenols and / or alkylphenol alkoxylates or no alkylphenols and / or alkylphenol alkoxylates are added to the hydrocarbon.

16. Hydrocarbons, reaction products of α-olefin / maleic anhydride copolymers with amino-hydroxy compounds; Solvent, and Contaminants A dispersant comprising:

17. 17. The dispersant of claim 16, wherein the dispersant comprises from about 1 ppm to about 10,000 ppm of the reaction product and from about 1 ppm to about 10,000 ppm of the solvent.

18. The reaction product has formula I: 【Chemistry 21】 wherein R is C ８ ~C ３６ an alkyl group, n is 5 to 200, and X is a linking group; 18. A dispersant according to claim 16 or 17.

19. 18. A dispersant according to claim 16 or 17, wherein the amino-hydroxy compound is a cyclic aliphatic compound, an acyclic aliphatic compound, or an aromatic compound.

20. The cyclic aliphatic compound is 【Chemical 22】 【Chemistry 23】 20. The dispersant of claim 19 selected from:

21. The acyclic aliphatic compound is 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemical 27】 【Chemistry 28】 【Chemical 29】 【Chemistry 30】 【Chemistry 31】 20. The dispersant of claim 19 selected from:

22. The aromatic compound is 【Chemistry 32】 【Chemical 33】 【Chemical 34】 【Chemistry 35】 【Chemical 36】 【Chemical 37】 【Chemical 38】 【Chemical Formula 39】 【Chemistry 40】 20. The dispersant of claim 19 selected from:

23. 18. A dispersant according to claim 16 or 17, wherein the dispersant is stable at temperatures from about 20°C to about 400°C.

24. 18. The dispersant of claim 16 or 17, wherein a hydrocarbon processing unit comprises the dispersant.

25. 18. The dispersant of claim 16 or 17, wherein the hydrocarbon comprises crude oil.

26. 18. The dispersant of claim 16 or 17, wherein the reaction product comprises a weight average molecular weight of from about 1,000 Da to about 100,000 Da.

27. X is an alkylene group, an arylene group, -CH ２ CH ２ N.H.C.H. ２ CH ２ -or-CH ２ CH ２ OCH ２ CH ２ The dispersant of claim 18, wherein

28. 18. The dispersant of claim 16 or 17, wherein the composition comprises a solvent selected from the group consisting of toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, ethylene glycol, ethylene glycol monobutyl ether, kerosene, propylene carbonate, glycol ethers, and any combination thereof.

29. 18. A dispersant according to claim 16 or 17, wherein the dispersant excludes alkylphenols and / or alkylphenol alkoxylates.

30. 18. A dispersant according to claim 16 or 17, wherein the α-olefin is branched or linear.

31. 18. A dispersant according to claim 16 or 17, wherein the reaction product does not comprise acid groups and / or the dispersant does not comprise compounds with acid groups.

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