Corrosion-inhibiting additives and methods of making and using same

Abstract

Additives and methods of making and using the additives are described. The additive can be provided as a concentrate for addition to one or more hydrocarbons in crude oil refining and processing facilities to inhibit corrosion of corrosive metal components in contact with the process stream. The additive can be made by reacting a glycerol-limited vegetable oil fatty acid with an amine, where the glycerol-limited vegetable oil fatty acid can be a hydrolyzed vegetable oil that has been at least partially refined to glycerol. The additive can be further reacted to provide an ammonium salt, which can be added to an aqueous composition to provide corrosion protection for corrosive surfaces in contact with the aqueous composition.

Description

[Technical Field]

[0001] The present invention relates to fatty amide additives and their combination with fatty ester additives, ammonium salts of fatty amide additives, and methods for making and using the additives.The additives are derived from glycerol-limited vegetable oil fatty acids and amine compounds.The additives can be used as corrosion inhibitors, for example, in the crude oil processing and refining industries, but can also be used as dispersants, lubricants, antifoaming agents, foaming agents, and release agents. [Background technology]

[0002] In 1861, early petroleum refineries converted crude oil into kerosene. Today, refinery processes typically involve processing and / or treating crude oil to provide not only kerosene but also a wide range of other products and product intermediates. While certain process steps, such as distillation, cracking, and removal of impurities and by-products, are common, the technologies adopted for the same process can vary considerably between refineries. Petroleum refining begins with desalting of the feedstock, which may be followed by distillation or fractionation of the hydrocarbon process stream into different hydrocarbon groups. Most distillation products are further converted into desired, more usable products or product intermediates by changing the size and structure of the hydrocarbon molecules through cracking, reforming, and other conversion processes. To eliminate unwanted components or improve product quality, these converted products and / or intermediates may then be subjected to various processing and separation processes, such as extraction, hydrotreating, and sweetening. Integrated refineries not only offer multiple separation and / or processing steps, such as fractionation, refining, treating, and blending operations, but such refineries may also include petrochemical processing.

[0003] The refinery industry relies heavily on certain critical materials, including carbon and alloy steels, copper, aluminum, and non-ferrous alloys, for the construction of petroleum refining equipment, such as pressure vessels, storage vessels, separation units, reaction vessels, pumps, sensors, valves, columns, boilers, heat exchangers, condensers, and pipelines. However, corrosion of these metallic components is a major cause of inefficiencies in the refining process, as it causes equipment deterioration, shortened service life, or even failure, which incurs significant annual costs for maintenance, operation, repair, replacement, and the like. Corrosion risk is generally increased by the high temperatures used in refining equipment.

[0004] Crude oil is a complex mixture of many different hydrocarbons and typically relatively small amounts of non-hydrocarbons. In addition to hydrocarbons, crude oil may contain sulfur-, chlorine-, nitrogen-, and oxygen-containing compounds as gaseous, liquid, and solid phases dissolved in the oil, as well as other organic materials. Many of these non-hydrocarbon components may be in the form of corrosives or corrosive precursors that attack refinery equipment.

[0005] Crude oil can be graded in two ways. The first is based on the proportion of organic compounds, such as paraffins, naphthenes, aromatics, or mixtures thereof. The second method of classifying crude oil is by American Petroleum Institute (API) gravity, which is generally inversely proportional to the density of the crude oil. The higher the API gravity, the lighter the crude oil. Low carbon, high hydrogen, and high API gravity crude oils are typically rich in paraffins and tend to produce a higher proportion of gasoline and light petroleum products. Low carbon, low hydrogen, and low API gravity oils are generally relatively rich in aromatics.

[0006] Crude oil may contain entrained water and / or brine. Corrosives may be present in the hydrocarbon and / or aqueous portions of crude oil. Corrosives that may be contained in crude oil include hydrogen chloride, organic and inorganic chlorides, hydrogen sulfide, mercaptans and / or other organic sulfur compounds, carbon dioxide, dissolved oxygen, water, organic acids, and / or nitrogen compounds.

[0007] Crude oil containing large amounts of hydrogen sulfide (H2S) is called "sour" crude oil, while crude oil containing less H2S is known as "sweet" crude oil.

[0008] Naphthenic acids are organic acids often present in crude oil and hydrocarbon streams during oil refining and processing. Naphthenic acids are corrosive to carbon steel and stainless steel, especially at high temperatures (e.g., above 260°C). Corrosion is greatly increased by the presence of naphthenic acids and / or sulfur compounds in high-temperature regions of distillation systems. The presence of some organic acids, such as formic acid, acetic acid, and propionic acid, can induce corrosion even at lower temperatures (e.g., below 260°C).

[0009] Corrosion inhibitors are widely used in the oil recovery and processing industry to control the costly problem of corrosion in oil refineries. Corrosion inhibitors and / or other types of additives may be diluted to some extent with a solvent or incorporated into corresponding formulations (also referred to as "compositions") that are used undiluted in their undiluted form. These formulations may also contain one or more other optional components, with or without a solvent. Thus, the term "additive formulation" refers to a composition containing one or more additives, optionally a solvent, and optionally one or more other components. Similarly, as used herein, a "corrosion inhibitor" is an additive that helps protect against corrosion. As used herein, a "corrosion inhibitor formulation" is a composition containing one or more corrosion inhibitors, optionally a solvent, and optionally one or more other components. Such additive and corrosion inhibitor formulations may be provided in a variety of forms, such as solids (e.g., powders, pellets, granules, blocks, etc.), liquids, dispersions, gels, putties, gases, and / or the like. Liquid, solution, dispersion, and gel embodiments of these formulations are more prone to stability issues related to phase separation.

[0010] Manufactured batches of additive formulations are typically stored for a period of time before use or further processing. During storage and / or transportation, it is desirable for the additive formulation to be stable against, for example, excessive phase separation into separate liquids, precipitation of solids and / or gels, sedimentation, or other undesirable phase separation. Additive formulations that exhibit such changes may require special treatment to return the additive formulation to its original state. In a practical manner, it may not even be possible to return the additive formulation to its original state; in its altered form, the additive formulation may not be usable. For example, in an additive formulation containing precipitate, the settled material may not be pumpable or pourable. In either case, excessive phase separation of the additive composition during storage or transportation is highly undesirable. In contrast, in some cases, phase separation during actual use in a refinery may be tolerable or even desirable if the additive is still able to provide the desired function, e.g., corrosion protection in the case of a corrosion inhibitor. In other cases, it may be desirable to protect against phase separation even during refinery use as well.

[0011] For addition to industrial process streams or batches, such as hydrocarbon-containing process streams or batches in petroleum refining operations, additive formulations may conveniently be provided in a variety of forms, such as in the form of a solution or dispersion in an organic solvent that is miscible with hydrocarbon petroleum streams, such as crude oil and other hydrocarbon petroleum streams. Because such solutions or dispersions of additives are typically shipped and stored, it may be economical if the solution or dispersion is relatively concentrated relative to the additive, thereby avoiding the extra expense associated with shipping and storing commodities such as organic solvents. Such solutions or dispersions offer flexibility in that they can be easily further diluted, if desired, at a more convenient time, such as at or near the point of use, yet can be used without further dilution if a higher concentration is desired. Summary of the Invention [Problem to be solved by the invention]

[0012] It is desirable that such solutions and / or dispersions, or more dilute formulations of additives, as well as the additives themselves, be sufficiently stable during storage, shipping, and use. Additive solutions, dispersions, and / or more dilute formulations are typically stored and / or transported in unheated winter environments that reach temperatures below, for example, 0° C., −10° C., −20° C., −30° C., or even −40° C. It would therefore be advantageous to find corrosion inhibitor and other additive formulations that do not undergo excessive phase separation and / or settling during storage, handling, or use, and that, when provided as solutions and / or dispersions in organic solvents, do not separate excessively, even when stored, handled, transported, or used at low temperatures. [Means for solving the problem]

[0013] The present inventors have discovered additive compositions with limited glycerol content that are more stable against phase separation. For example, additive compositions incorporating one or more additives derived from vegetable oil fatty acids, such as soybean oil fatty acids, are more stable against phase separation when the vegetable oil fatty acid content has a reduced glycerol content. In a preferred embodiment, the additive composition with improved stability incorporates one or more additives derived from glycerol-limited soybean oil fatty acids. In other embodiments, the formulation or one or more components thereof can be processed to remove at least a portion of the glycerol content, thereby improving stability against phase separation.

[0014] The inventors have also discovered that compositions of additives in organic solvents when made from glycerol-limited vegetable oil fatty acids are more stable to precipitation (i.e., exhibit little or no precipitation) over a period of three weeks when stored at temperatures such as 0°C to -10°C than equivalent concentrates made from tall oil fatty acids.

[0015] In one aspect, an additive composition is provided comprising a plurality of amides and / or ammonium salts thereof, wherein at least a portion of the plurality of amides comprise a reaction product derived from a first set of reactants comprising one or more glycerol-limited vegetable oil fatty acids and a polyamine, wherein the one or more glycerol-limited vegetable oil fatty acids comprise 0 weight percent to 0.1 weight percent glycerol based on the total weight of the one or more glycerol-limited vegetable oil fatty acids, and the polyamine comprises a polyamine having the formula NH(CHCHNH)CHCHNH, where x is 0 to 100. For example, if the one or more glycerol-limited vegetable oil fatty acids consist of 0.06 parts by weight glycerol and 100 parts by weight soybean oil fatty acids, then the total weight of the glycerol-limited soybean oil fatty acids is 100.06 parts by weight and the glycerol content is 0.06 / 100.06 × 100% = 0.06%. The amides and / or ammonium salts thereof, in some embodiments, function as corrosion inhibitor additives in the additive composition to help protect against corrosion.

[0016] In a further aspect, a combination additive composition is provided comprising a plurality of amides and / or ammonium salts thereof, and further comprising a plurality of esters, wherein at least a portion of the plurality of amides comprises a first reaction product derived from a first set of reactants comprising one or more glycerol-limited vegetable oil fatty acids and a polyamine, wherein the one or more glycerol-limited vegetable oil fatty acids comprise 0 weight percent to 0.1 weight percent glycerol, based on the total weight of the one or more glycerol-limited vegetable oil fatty acids, and the polyamine comprises, consists of, or consists essentially of a polyamine having the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is between 0 and 100. At least a portion of the esters comprise a second reaction product derived from a second set of reactants comprising a second glycerol-limited vegetable oil fatty acid(s) and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxyl group, and the second glycerol-limited vegetable oil fatty acid(s) comprising 0 to 0.1 weight percent glycerol, based on the total weight of the second glycerol-limited vegetable oil fatty acid(s). Individually, the amides and esters, and compositions containing the amides or esters, can each be used in a variety of applications, such as to inhibit corrosion. However, combinations of amides and esters, and compositions containing the combinations, are particularly effective for inhibiting corrosion.

[0017] In a further aspect, a composition is provided comprising a heavy aromatic naphtha and an additive comprising a plurality of amides and / or ammonium salts thereof, wherein at least a portion of the plurality of amides comprises a reaction product derived from a first set of reactants comprising one or more glycerol-limited vegetable oil fatty acids and a polyamine, wherein the one or more glycerol-limited vegetable oil fatty acids comprise 0 weight percent to 0.1 weight percent glycerol, based on the total weight of the one or more glycerol-limited vegetable oil fatty acids, and the polyamine has the formula NH(CHCHNH)CHCHNH, where x is 0 to 100. The reaction product derived from the first set of reactants can conveniently be synthesized in the heavy aromatic naphtha to provide the composition, and / or the heavy aromatic naphtha can be added to the reaction product after synthesis to form the composition. The composition comprising the heavy aromatic naphtha is in a convenient form for addition to one or more hydrocarbons to impart desirable properties, such as corrosion inhibition, antifouling properties, and / or other desirable properties. Heavy aromatic naphtha is generally miscible with hydrocarbons, and therefore, when added to one or more hydrocarbons, the composition can disperse in the one or more hydrocarbons, thereby imparting improved characteristics.

[0018] In a further aspect, a composition is provided comprising heavy aromatic naphtha, a plurality of amides and / or ammonium salts thereof, and further comprising a plurality of esters, wherein at least a portion of the plurality of amides comprises a first reaction product derived from a first set of reactants comprising a first one or more glycerol-limited vegetable oil fatty acids and a polyamine, wherein the first one or more glycerol-limited vegetable oil fatty acids comprise 0 weight percent to 0.1 weight percent glycerol, based on the total weight of the first one or more glycerol-limited vegetable oil fatty acids, and the polyamine comprises a polyamine having the formula NH(CHCHNH)CHCHNH, where x is 0 to 100. At least a portion of the esters comprise a second reaction product derived from a second set of reactants comprising a second glycerol-limited vegetable oil fatty acid(s) and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxyl group, and the second glycerol-limited vegetable oil fatty acid(s) comprising 0 to 0.1 weight percent glycerol, based on the total weight of the second glycerol-limited vegetable oil fatty acid(s). Individually, the amides, ammonium salts thereof, and esters, and compositions containing them, can each be used in a variety of applications, such as for corrosion inhibition. However, combinations of amides and esters, and compositions containing the combinations, are particularly effective for corrosion inhibition.

[0019] In a further aspect, there is provided a composition comprising greater than 5 weight percent water, based on the total weight of the composition, and an additive comprising an ammonium salt of a plurality of amides, wherein at least a portion of the plurality of amides comprise a reaction product derived from a set of reactants including one or more glycerol-limited vegetable oil fatty acids and a polyamine, wherein the one or more glycerol-limited vegetable oil fatty acids comprise from 0 weight percent to 0.1 weight percent glycerol, based on the total weight of the one or more glycerol-limited vegetable oil fatty acids, and the polyamine has the formula NH(CHCHNH)CHCHNH, where x is from 0 to 100. The ammonium salt may be more water-soluble and / or water-dispersible than the amides, and therefore the composition is particularly useful for adding to aqueous materials to impart desired properties to the composition, such as corrosion-inhibiting or dispersing properties in aqueous systems.

[0020] In a further aspect, a hydrocarbon composition is provided comprising one or more hydrocarbons and at least one additive composition incorporated into the one or more hydrocarbons, wherein the at least one additive composition is selected from an amide composition, an ester composition, and combinations thereof. the amide composition comprises a plurality of amides, at least a portion of which comprise a first reaction product derived from a first set of reactants comprising a first one or more glycerol-limited vegetable oil fatty acids and a polyamine, wherein the first one or more glycerol-limited vegetable oil fatty acids comprise from 0 weight percent to 0.1 weight percent glycerol, based on the total weight of the first one or more glycerol-limited vegetable oil fatty acids, and the polyamine has the formula NH(CHCHNH)CHCHNH, where x is from 0 to 100; the ester composition comprises a plurality of esters, at least a portion of which comprise a second reaction product derived from a second set of reactants comprising a second one or more glycerol-limited vegetable oil fatty acids and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxyl group; and the second one or more glycerol-limited vegetable oil fatty acids comprise from 0 weight percent to 0.1 weight percent glycerol, based on the total weight of the second one or more glycerol-limited vegetable oil fatty acids. Incorporation of the additive composition into one or more hydrocarbons may impart corrosion-inhibiting properties to the combination of the one or more hydrocarbons and the additive composition, or may inhibit or ameliorate corrosion of metal components in contact with the one or more hydrocarbons from corrosive substances in the hydrocarbons.

[0021] In a further aspect, there is provided a method for providing corrosion protection for a surface in contact with one or more hydrocarbons, the method comprising combining a corrosion inhibitor composition with the one or more hydrocarbons, the corrosion inhibitor composition comprising a plurality of amides and / or ammonium salts thereof, at least a portion of the plurality of amides comprising a reaction product derived from a first set of reactants comprising one or more glycerol-limited vegetable oil fatty acids and a polyamine, the one or more glycerol-limited vegetable oil fatty acids comprising 0 weight percent to 0.1 weight percent glycerol based on the total weight of the one or more glycerol-limited vegetable oil fatty acids, and the polyamine having the formula NH(CHCHNH)CHCHNH, where x is 0 to 100. The method is useful, for example, in petroleum or other hydrocarbon industrial processing facilities, where addition of the corrosion inhibitor composition to the one or more hydrocarbons can inhibit corrosion of metal components in contact with the one or more hydrocarbons.

[0022] In a further aspect, a method of making an additive composition is provided, the additive composition comprising a first reaction product. The method includes combining one or more glycerol-limited vegetable oil fatty acids with a polyamine to form a first reaction mixture, the one or more glycerol-limited vegetable oil fatty acids comprising 0% to 0.1 wt. % glycerol, based on the total weight of the one or more glycerol-limited vegetable oil fatty acids; optionally adding a hydrocarbon solvent to the first reaction mixture; and heating the first reaction mixture at a reaction temperature and for a period of time effective to form water and a first reaction product, the first reaction product comprising a plurality of amides. The additive composition is useful, for example, for addition to hydrocarbon process streams and batches in industrial processes to impart corrosion-inhibiting properties.

[0023] In a further aspect, a method of making a combination additive composition includes combining a first one or more glycerol-limited vegetable oil fatty acids with a polyamine to form a first reaction mixture, wherein the first one or more glycerol-limited vegetable oil fatty acids comprise 0% to 0.1% by weight of glycerol, based on a total weight of the first one or more glycerol-limited vegetable oil fatty acids; optionally adding a hydrocarbon solvent to the first reaction mixture; and heating the first reaction mixture at a reaction temperature and for a period of time effective to form water and a first reaction product, wherein the first reaction product is a plurality of amides. and combining components comprising the first and second reaction products to form a combined additive composition. The combination of the first and second reaction products, as well as compositions comprising the combination, is useful, for example, as corrosion inhibitors for addition to hydrocarbon streams to impart corrosion-inhibiting properties. DETAILED DESCRIPTION OF THE INVENTION

[0024] While this disclosure provides reference to various embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the present application. Various embodiments are described in detail with reference to the drawings. Reference to various embodiments does not limit the scope of the claims appended hereto. Additionally, any examples set forth in this application are illustrative and not intended to be limiting, merely describing some of the many possible embodiments of the appended claims.

[0025] definition

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of this application, the methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety and for all purposes.

[0027] As used herein, the terms "comprise(s)," "include(s)," "having," "has," "can," "contain(s)," and variations thereof are intended to be open-ended transitional phrases, terms, or words that do not exclude the possibility of additional acts or structures. The singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise.

[0028] As used herein, the term "optional" or "optionally" means that the subsequently described material, condition, feature, event, or circumstance may occur but need not occur, and that its use includes instances where the material, condition, feature, event, or circumstance occurs and instances where it does not occur.

[0029] As used herein, any recited range of values ​​should be construed as supporting claims that contemplate all values ​​within the range and that recite any subranges having endpoints that are real values ​​within the recited range. As an example, a disclosure herein of a range of 1 to 5 is intended to support claims of any of the following ranges: 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, 2 to 3, 3 to 5, 3 to 4, and 4 to 5, and fractions thereof, e.g., 1.5 to 3.5, 1.7 to 4.8, etc.

[0030] As used herein, a combination of fatty acids that can be produced by hydrolysis of a single type of vegetable oil is referred to as a "vegetable oil fatty acid." Because a single type of vegetable oil contains esters of various fatty acids, hydrolysis of the vegetable oil produces a combination of fatty acids. For example, hydrolysis of soybean oil can produce "soybean oil fatty acids" in combination with the by-product glycerol. Although used in the singular, soybean oil fatty acids contain a combination of different fatty acid compounds rather than a single fatty acid compound. Vegetable oils are natural products and can vary in composition, for example, with respect to the relative content of various fatty acid compounds in the form of esters. However, the type and range of each fatty acid compound in a vegetable oil fatty acid is generally characteristic of the type of vegetable oil from which the vegetable oil fatty acid is derived. While the singular "vegetable oil fatty acid" refers to a combination of fatty acid compounds that can be produced by hydrolysis of the named vegetable oil, "vegetable oil fatty acid" as used herein refers to a combination of fatty acids that can be produced by hydrolysis of a combination of two or more types of vegetable oils.

[0031] As used herein, the term "glycerol-limited" with respect to a material generally means that the material contains no more than 0.1 weight percent glycerol based on the weight of the material (including glycerol, if present). For example, "glycerol-limited fatty amides" refers to a material that contains fatty amides, where the material contains no more than 0.1 weight percent glycerol based on the weight of the glycerol-limited fatty amides.

[0032] The term "glycerol-limited vegetable oil fatty acids" refers to a mixture containing 0.1% or less glycerol by weight of the mixture and 99% or more fatty acids by weight. Glycerol-limited vegetable oil fatty acids can be produced by various means. One commercially important means of producing glycerol-limited vegetable oil fatty acids is by hydrolysis of the named vegetable oil and subsequent refining to remove glycerol, a by-product of hydrolysis. The types of fatty acids and their proportions in glycerol-limited vegetable oil fatty acids depend on the composition of the hydrolyzed vegetable oil, particularly the type of vegetable oil, i.e., the type of plant from which the vegetable oil is derived. For example, soybean oil, as a natural product, can vary in composition with respect to fatty acid esters, but within the ranges characteristic of soybean oil. However, in principle, glycerol-limited vegetable oil fatty acids can also be produced by combining the correct types of fatty acids in the correct proportions, with the cumulative glycerol content, if any, being sufficiently low so that the resulting mixture is glycerol-limited as defined in accordance with the present invention. In such embodiments, since the fatty acid material is initially suitably glycerol-limited, no degree of refining to reduce the glycerol content is required. For illustrative purposes only, a glycerol-limited soybean oil fatty acid may, in a particular example, comprise 10% palmitic acid, 4% stearic acid, 23% oleic acid, 51% linoleic acid, and 9% alpha-linolenic acid by weight, based on the total weight of fatty acids. Such a glycerol-limited soybean oil fatty acid may, in principle, be produced by combining 10 parts palmitic acid, 4 parts stearic acid, 23 parts oleic acid, 51 parts linoleic acid, 9 parts alpha-linolenic acid, and any other component of a glycerol-limited soybean oil fatty acid, with the glycerol in such a glycerol-limited soybean oil fatty acid being limited as supplied, or the mixture being refined to remove the glycerol.

[0033] As used herein, "hydrolyzed vegetable oil" and similar terms, including specific vegetable oil names, refer to compositions produced by hydrolysis of vegetable oils. For example, a composition containing soybean oil fatty acids and glycerol that can be produced by hydrolysis of soybean oil is referred to herein as "hydrolyzed soybean oil."

[0034] As used herein, "polyamine," "polyamine," and "polyamine" are understood to refer to distinct compounds having a single molecular weight, such as tetraethylenepentamine (HNCHCHNHCHCHNHCHNHCHCHNHCHNHCHNHCHNH), as well as combinations of individual polyamine compounds. For example, a polyamine may have the formula NH(CHCHNH)CHCHNH, where x is 0 to 100. In this particular example, the number x is an integer when the polyamine is a distinct polyamine compound, but x can also be a fractional or mixed number when the polyamine is a mixture of distinct polyamine compounds having different molecular weights. As used herein, the term "polyamine" is not used solely to refer to distinct polyamine compounds, but can also refer to mixtures and / or combinations of distinct polyamine compounds. A polyamine may contain two or more, even three or more, even four or more, or even five or more amine moieties. The amine moieties can be primary, secondary, and / or tertiary.

[0035] As used herein, the term "concentrate" generally refers to a composition in which the concentration of an additive in the composition is greater than the concentration of such additive after the composition is diluted for its intended use. Concentrates can be solids, liquids, dispersions, gels, or gases. Concentrates may or may not contain solvent until further diluted. In exemplary embodiments, concentrates may contain 0 to 80 parts, or even 0 to 50 parts, or even 0 to 25 parts, or even 0 to 10 parts of solvent per 100 parts by weight of additive before dilution with solvent. If desired, concentrates may be diluted by adding an amount of additional solvent, which may be the same and / or different from the solvent in the concentrate. By way of example, dilution may be performed by adding 1 to 1000, or even 10 to 500, or even 10 to 100 parts by weight of additional solvent per 50 to 100 parts by weight of solvent in the concentrate.

[0036] All reaction schemes herein are for purposes of illustrating the reactants and reaction products.

[0037] Consideration

[0038] For example, in oil refining, commercial practice involves the use of fatty amides as corrosion inhibitors or other types of additives. Traditionally, fatty amides have been made by reacting tall oil or tall oil fatty acids with amines. Tall oil and tall oil fatty acid (TOFA) have been convenient sources of fatty acids. Tall oil is a by-product of the Kraft process for wood pulp production. Crude tall oil typically contains rosin, which contains resin acids (primarily abietic acid and its isomers); a mixture of fatty acids (primarily palmitic acid, oleic acid, and linoleic acid); fatty alcohols; sterols; and other alkyl hydrocarbon derivatives. Tall oil fatty acid is a refined form of tall oil and contains a lower weight percent of rosin (1 to 10 weight percent) than tall oil. Tall oil fatty acid contains fatty acids, primarily oleic acid.

[0039] Tall oil fatty acid (TOFA) can be reacted with one or more amines to produce TOFA amides, a reaction product that contains a mixture of fatty amides as well as other components resulting from the resin acids in TOFA. The reaction can be summarized as follows: Scheme 1 TOFA + amine → mixture of fatty amides + other ingredients + water

[0040] TOFA-derived fatty amides can find use, for example, as corrosion inhibitor additives in hydrocarbon streams during crude oil refining or other processing. Conveniently, additive compositions incorporating such additives into hydrocarbon streams can be provided as concentrates in organic solvents. The concentrates can be stored, shipped, or delivered to oil processing plants, either neat or in diluted form, for addition to the hydrocarbon stream. However, even concentrates or diluted forms of such additives can be unstable when stored at low temperatures, e.g., below 0°C, -10°C, or -20°C, for periods of days or weeks, exhibiting precipitation, other phase separation, or other instability such that the affected composition cannot be easily redissolved or redispersed. For example, corrosion inhibitor compositions incorporating the reaction product of TOFA and 2-aminoethylethanolamine (AEEA) exhibited precipitation after only a few days at 0°C, -10°C, or -20°C. Storage at -10°C or -20°C for extended periods, e.g., 64 days, resulted in a precipitate that could not be redissolved even after warming to room temperature (15-25°C or approximately 20°C). Thus, even concentrated or diluted forms of conventionally used TOFA-derived corrosion inhibitors may be less stable than desired at cooler temperatures. Without being bound by theory, the inventors speculate that this instability may be a direct or indirect result of the rosin content in TOFA.

[0041] Although rosin acid content can be removed using separation techniques, further drawbacks are very difficult to overcome. It is becoming increasingly difficult to obtain tall oil or TOFA materials from commercial sources at economically viable prices. Therefore, it is becoming increasingly desirable to find fatty amide materials that can be more easily sourced as replacements for tall oil or TOFA materials.

[0042] Fatty amides can also be made by reacting vegetable oils with one or more amines. Vegetable oils contain glycerides, primarily triglycerides. Glycerides are esters of glycerol (propane-1,2,3-triol) and fatty acids. Fatty amides derived from vegetable oils show great potential as corrosion inhibitors to replace fatty amides derived from tall oil or TOFA. One advantage is that fatty amides derived from one or more vegetable oils can provide excellent corrosion protection and, as natural substances, contain minimal, if any, rosin acid. Unfortunately, a technical challenge to the use of such materials relates to stability. The inventors have found that additives made from vegetable oils and incorporating glycerol tend to have poor stability in that they undergo phase separation.

[0043] Importantly, the practice of the present invention provides a technical solution that provides vegetable oil-derived fatty amides that are much more stable. As a result, the fatty amide materials of the present invention can be used as a replacement for all or part of previously used tall oil and TOFA materials.

[0044] Because vegetable oils contain a mixture of glycerides, the reaction of even a single type of amine will result in a mixture of fatty amides. The general reaction between vegetable oils and amines can be summarized as follows, with glycerol being the by-product: Scheme 2 Vegetable oil + amine → fatty amide + glycerol mixture

[0045] Alternatively, one or more vegetable oils may be hydrolyzed to produce hydrolyzed vegetable oils containing a mixture of fatty acids and the by-product glycerol. The hydrolyzed vegetable oils (fatty acids and glycerol) can then be reacted with amines to produce fatty amides in combination with glycerol. The reaction can be summarized as follows: Scheme 3 (i) Vegetable oil + water → Hydrolyzed vegetable oil (a mixture of fatty acids and glycerol) (ii) Hydrolyzed vegetable oil + amine → fatty amide + glycerol + water mixture

[0046] Other components may be present in Schemes 2 and 3. For example, the hydrolysis of vegetable oils represented by Scheme 3, reaction (i) may be catalyzed by acids or bases. It will be further understood that, depending on the pH, the fatty acids may be present as their salts.

[0047] As can be seen from Schemes 2 and 3, the production of fatty amide additives from vegetable oils provides reaction products containing glycerol.The reaction products of vegetable oils and amines may be prone to phase separation.Without wishing to be bound by theory, the inventors believe that the presence of the by-product glycerol in the intermediate and then the fatty amide product makes the additive composition more prone to phase separation than a similar additive composition that has been at least partially refined for glycerol, thus resulting in an additive composition with lower stability.In other words, when vegetable oil-derived fatty amide additives are used in additive compositions, the use of additive compositions with reduced glycerol content improves stability.

[0048] In accordance with the present invention, glycerol-reduced fatty amide additives can be made, for example, according to the reaction illustrated in Scheme 4a: Scheme 4a (i) Vegetable oil + water → Hydrolyzed vegetable oil (fatty acids + glycerol) (ii) Hydrolyzed vegetable oil-glycerol → glycerol-limited vegetable oil fatty acids (VOFAs) (iii) Glycerol-limited vegetable oil fatty acids + polyamines → Glycerol-limited vegetable oil fatty acid amide + water

[0049] For example, as shown in Scheme 4b, the glycerol-limited fatty amide reaction products of tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2NH2) (TEPA) with glycerol-limited soybean oil fatty acids are much more stable and resistant to phase separation than the fatty amides made by Schemes 2 and 3. Scheme 4b (i) Soybean oil + water → Hydrolyzed soybean oil (fatty acids + glycerol) (ii) Hydrolyzed soybean oil-glycerol → glycerol-limited soybean oil fatty acid (SOFA) (iii) Glycerol-limited soybean oil fatty acid + tetraethylenepentamine → glycerol-limited soybean oil fatty acid amide + water

[0050] Glycerol-limited soybean oil fatty acids (SOFA) are commercially available.

[0051] Glycerol-limited vegetable oil fatty acids, including those derived from soybean oil, can be produced according to Scheme 4a(i)-(ii) by the following procedure: adding an alkali, such as aqueous sodium hydroxide and / or aqueous potassium hydroxide, to one or more vegetable oils, such as soybean oil, to produce a mixture thereof. The mixture can be heated to a suitable temperature (e.g., 30°C to 100°C, e.g., 30°C to 100°C, or 40°C to 90°C, or 50°C to 100°C, or 60°C to 100°C, or 50°C to 90°C, or 50°C to 80°C, or 50°C to 70°C, or 55°C to 65°C, or about 60°C) for a suitable time (e.g., 1 hour to 24 hours, e.g., 1 hour to 10 hours, or 2 hours to 7 hours, or 3 hours to 6 hours, or 3 hours to 5 hours, or about 4 hours) effective to cause saponification of the one or more vegetable oils to a desired degree of completion. Hydrolysis of one or more vegetable oils, known as saponification, produces fatty acid salts and the by-product glycerol. To produce free fatty acids from the fatty acid salts, the pH of the mixture is reduced by adding a mineral acid, such as sulfuric acid, hydrochloric acid, or a combination thereof. For example, the pH may be reduced to 1-4, or 1-3, or to about 2. The aqueous phase, containing water, mineral acid salts, and glycerol, separates into a separate layer from the organic phase, which is then separated from the organic phase. The organic phase may be dried. The organic phase may be further purified by separation into fractions, each having a different range of acid value. For the present invention, the glycerol-limited vegetable oil fatty acids may be derived from a fraction having an acid value of 170-230 mg KOH / g, or 180-220 mg KOH / g, or 190-210 mg KOH / g, or about 192-205 mg KOH / g. For example, the glycerol-limited vegetable oil fatty acid can comprise, consist of, or consist essentially of a glycerol-limited soybean oil fatty acid having an acid number of from about 192 to about 205 mg KOH / g.

[0052] Without wishing to be bound by theory, it is believed that the glycerol in the hydrolyzed soybean oil and / or its reaction products destabilizes the resulting additive composition. Thus, at least partially removing the glycerol content from the component or its precursor provides an additive composition with improved stability.

[0053] In a further embodiment of the present invention, disclosed herein is a combination additive composition comprising a mixture of the glycerol-limited fatty amide additive of Scheme 4a or 4b in combination with multiple fatty esters. For improved stability, the fatty esters are preferably also glycerol-limited to the same reduced concentration range as the glycerol-limited fatty amides of Scheme 4a and 4b. The combination additive composition of the present invention is useful in the oil processing and refining industries for applications similar to those of the amides, for example, to protect against corrosion.

[0054] For example, fatty esters can be made by transesterification, as shown in Scheme 5. Scheme 5 Vegetable oil + alcohol → glycerol + multiple esters

[0055] Scheme 5 shows that fatty esters can generally be made by reacting one or more vegetable oils with one or more alcohols in a transesterification reaction. A preferred vegetable oil is soybean oil.

[0056] Alcohols suitable for Scheme 5 can be primary, secondary, tertiary, or mixtures thereof. Preferred alcohols contain at least one nitrogen atom and multiple OH groups, or even 2 to 6, or even 2 to 4, or even 3 alcohol groups. A more preferred alcohol is triethanolamine (TEA), which contains three ethanol moieties (each containing a primary OH group) attached to a central N atom.

[0057] However, the reaction product of Scheme 5 again contains glycerol. Practice of the present invention teaches that all or a portion of the glycerol may be removed to improve the stability of additive compositions incorporating the fatty ester product. As a result, in the practice of the present invention, the product mixture of Scheme 5 may be at least partially purified relative to glycerol to provide the glycerol-limited fatty esters of the present invention.

[0058] Alternatively, a preferred method of making multiple fatty esters is by reaction of an alcohol with one or more glycerol-limited vegetable oil fatty acids, e.g., hydrolyzed vegetable oil refined to glycerol, as illustrated in Scheme 6, where an exemplified vegetable oil is soybean oil and an exemplified alcohol is triethanolamine: Scheme 6 (i) Soybean oil + water → Hydrolyzed soybean oil (soybean oil fatty acids + glycerol) (ii) Hydrolyzed soybean oil-glycerol → glycerol-limited soybean oil fatty acids (SOFA) (iii) Glycerol-limited soybean oil fatty acids + triethanolamine → SOFA-TEA ester additive + water

[0059] When carrying out Scheme 6(iii), the general reaction of a fatty acid (represented by RCOOH) with the triol triethanolamine to form a fatty ester can be represented in Scheme 7 as follows (where each R independently represents a linear, branched, or cyclic hydrocarbyl group):

[0060] [ka]

[0061] As shown in Scheme 7, even the reaction of a single specific fatty acid with a symmetric triol, such as triethanolamine, can produce three different esters. Furthermore, because glycerol-limited vegetable oil fatty acids, such as glycerol-limited soybean oil fatty acids, contain a mixture of fatty acids, the reaction of glycerol-limited vegetable oil fatty acids with TEA is expected to produce a more complex mixture of mono-, di-, and triester reaction products. The use of diols, tetrols, or other alcohols containing multiple OH groups also results in a product mixture. If the alcohol has at least one chiral carbon, the product mixture may be even more complex, as it can produce even more mono-, di-, tri-, etc. ester products.

[0062] The esterification reaction between glycerol-limited soybean oil fatty acids (SOFA, which contains a mixture of fatty acids) and triethanolamine (TEA) can be represented as follows: Scheme 8 SOFA + triethanolamine-H2O → SOFA-TEA ester (ester mixture)

[0063] The methods of making the additives disclosed herein can provide fatty amide and / or fatty ester reaction products that contain little or no glycerol, no rosin acids and / or their derivatives, and little or no reaction products of glycerol and resin acids, e.g., 0.1 weight percent (wt. percent) or less, based on the weight of the corresponding additive. The methods use glycerol-limited vegetable oil fatty acids, which are reacted with amines to produce fatty amides with limited glycerol content. The use of glycerol-limited vegetable oil fatty acids in the methods herein can produce additives with limited glycerol content (e.g., 0.1 wt. percent or less glycerol, based on the total weight of the fatty acid content).

[0064] In contrast to tall oil or tall oil fatty acids, the use of glycerol-limited vegetable oil fatty acids avoids rosin acid content, such as rosin acid or its derivatives. Rosin acid content is a natural component of tall oil and tall oil fatty acids. Because of their acidity, rosin acids can have a tendency to become corrosive in refinery equipment. Therefore, avoiding rosin acid is highly desirable. Advantageously, soybean oil and many other vegetable oils have little, if any, rosin acid content. As a result, fatty amides and fatty esters derived from soybean oil and other vegetable oils avoid the corrosion risks associated with rosin acid. Unfortunately, however, vegetable oil-derived additives are prone to phase separation, thereby reducing the attractiveness of using such additives. However, the present invention teaches how the stability of these materials can be improved to make their use practical and desirable. An important result is that the present invention not only avoids rosin acid corrosives, but also allows more stable vegetable oil-derived materials to be used for corrosion protection.

[0065] First aspect of the present invention

[0066] These embodiments illustrate glycerol-limited fatty acid amides that can be derived from one or more vegetable oils and then used as additives in additive compositions for a variety of purposes, such as corrosion protection in oil refineries or other environments where corrosion protection is desirable. Accordingly, in a first aspect of the present invention, a first additive composition is provided. The first additive composition comprises, consists of, or consists essentially of a first reaction product. The first additive composition can comprise, consist of, or consist essentially of the first reaction product and one or more solvents. The first additive composition can comprise, consist of, or consist essentially of the first reaction product and one or more optional ingredients. The first additive composition can comprise, consist of, or consist essentially of the first reaction product, one or more solvents, and further optional ingredients. Further optional ingredients may be selected from a wide range of materials, including, but not limited to, one or more of polymerization inhibitors, antioxidants, amines, foaming agents, dispersants, and phenol-formaldehyde polymers.

[0067] The first reaction product comprises, consists of, or consists essentially of a plurality of amides.

[0068] Amides can be synthesized by reacting a first set of reactants to produce a first reaction product and water, as shown in Scheme 9, where the glycerol-limited vegetable oil fatty acid is represented by VOFA and -HO represents removal of water during and / or after the reaction: Scheme 9 VOFA + polyamine (+ optional solvent(s)) - HO ---- → First Reaction Product (+Optional Solvent(s))

[0069] As depicted in Scheme 9, the reaction can be carried out without the addition of a solvent, or optionally in one or more solvents. If the reaction is carried out in one or more solvents, then the first additive composition comprises, consists of, or consists essentially of the first reaction product and one or more solvents. Regardless of whether the reaction is carried out in a solvent, a solvent or additional solvents can be added to the reaction product later to form a concentrate, as described in the third aspect of the present invention below. The one or more solvents can be selected from hydrocarbons. The hydrocarbons can be selected from one or more of aromatic compounds, alkanes, any type of naphtha, and alkenes. Examples of suitable hydrocarbons include, but are not limited to, one or more of benzene, toluene, xylene (o-xylene, m-xylene, p-xylene, and any combination thereof), heavy aromatic naphtha (HAN), C5-C17 alkanes, alkenes, and naphtha.

[0070] The first set of reactants comprises, consists of, or consists essentially of one or more glycerol-limited vegetable oil fatty acids and polyamines.

[0071] The first reaction product can comprise, consist of, or consist essentially of amides, or the first reaction product can comprise, consist of, or consist essentially of amides and one or more by-products. The first reaction product, with or without an optional solvent, is preferably used without further purification to provide the first additive composition. The use of glycerol-limited vegetable oil fatty acids in the present invention advantageously provides a first reaction product that is glycerol-free or contains less than 0.1 weight percent glycerol, based on the weight of the first reaction product, without further purification of the first reaction product.

[0072] As depicted in Scheme 4a(iii), reaction of a polyamine with a glycerol-limited vegetable oil fatty acid can produce a glycerol-limited vegetable oil fatty acid amide and by-product water. The glycerol-limited vegetable oil fatty acid amide comprises, consists of, or consists essentially of a plurality of amides. The first reaction product can consist of, consist essentially of, or the first reaction product can comprise, consist of, or consist essentially of amides and by-products and / or other materials. The first reaction product may comprise about 99 to 100 weight percent amide, or about 95 to 100 weight percent amide, or about 98 to 100 weight percent amide, or about 97 to 100 weight percent amide, or about 96 to 100 weight percent amide, or about 95 to 99.5 weight percent amide, or about 96 to 99.5 weight percent amide, or about 97 to 99.5 weight percent, or about 98 to 99.5 weight percent, or about 99 to 99.5 weight percent amide, or about 90 to 100 weight percent, or about 80 to about 100 weight percent, or about 90 to about 99.5 weight percent, or about 80 to about 99.5 weight percent amide, based on the weight of the first reaction product.

[0073] Preferably, by-product water is separated from the glycerol-limited vegetable oil fatty acid amide. Advantageously, at least a portion, or even most or all, of the by-product water can be removed during the reaction. Removal of water during the reaction helps the amide-forming reaction proceed. Thus, the dried first reaction product can comprise, consist of, or essentially consist of multiple amides and any by-products (if present). In this context, "essentially consisting of" allows for the presence of small amounts of water in the amide, and even when in a dry or partially dried state, the amide may contain small amounts of residual water from the reaction and / or some water absorbed from the environment. The first reaction product may comprise about 0 weight percent to 1 weight percent water, or about 0 weight percent to 5 weight percent water, or about 0 weight percent to 2 weight percent water, or about 0 weight percent to 3 weight percent water, or about 0 weight percent to 4 weight percent water, or about 0.5 weight percent to 5 weight percent water, or about 0.5 weight percent to 4 weight percent water, or about 0.5 weight percent to 3 weight percent, or about 0.5 weight percent to 2 weight percent, or about 0.5 weight percent to 1 weight percent water, or about 0 weight percent to 10 weight percent, or about 0 weight percent to about 20 weight percent, or about 0.5 weight percent to about 10 weight percent, or about 0.5 weight percent to about 20 weight percent water, based on the weight of the plurality of amides.

[0074] Preferably, the first reaction product contains mostly or exclusively amides, no or minimal glycerol, no or minimal rosin acids, no or minimal imidazoline content, and no or minimal water. The first reaction product may contain from 0 to 1 weight percent, or from 0 to 2 weight percent, or from 0 to 3 weight percent, or from 0 to 4 weight percent, or from 0 to 5 weight percent, or from 0 to 0.1 weight percent, or from 0 to 0.01 weight percent, or from 0 weight percent to 0.01 weight percent, or from 0 weight percent to 0 weight percent of each of the following types of materials, based on the weight of the total fatty amide content in the first reaction product: rosin acids, salts of rosin acids, amides of rosin acids, esters of rosin acids, fatty acid esters, imidazolines, and C1-C10 monohydric alcohols.

[0075] The first reaction product can be used without further purification to provide the first additive, may be further purified before use, or additional materials, such as additional fatty acid amides, may be added to the first reaction product to provide the first additive, provided that the additional materials are free of rosin acid and its derivatives and contain less than 0.1 weight percent glycerol based on the weight of the additional materials.

[0076] The first set of reactants can comprise, consist of, or consist essentially of one or more glycerol-limited vegetable oil fatty acids and polyamines. Preferred polyamines contain at least one primary amine moiety and at least one secondary polyamine moiety. Suitable polyamines can be linear, branched, or cyclic, and can be aliphatic or aromatic. Preferred polyamines have a linear carbon backbone and are aliphatic.

[0077] In preferred embodiments, the polyamine comprises a linear carbon backbone and includes at least one terminal primary amine moiety, and preferably a terminal primary amine moiety at each end, and one or more secondary and / or tertiary amine moieties pendant from the carbon backbone. In preferred embodiments, the polyamine may have the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is 0 to 100, or 0 to 90, or 0 to 80, or 0 to 70, or 0 to 60, or 0 to 50, or 0 to 40, or 0 to 30, or 0 to 20, or 0 to 10, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, or 0 to 1, or 1 to 5, or 2 to 4, or x is 3. In any of the embodiments and aspects herein, the polyamine may comprise, consist of, or consist essentially of tetraethylenepentamine (TEPA), (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2NH2).

[0078] The one or more glycerol-limited vegetable oil fatty acids used to make the amide in Scheme 9 can be selected from one or more of glycerol-limited avocado oil fatty acids, canola oil fatty acids, palm kernel oil fatty acids, corn oil fatty acids, cottonseed oil fatty acids, grape seed oil fatty acids, hazelnut oil fatty acids, hemp seed oil fatty acids, linseed oil fatty acids, olive oil fatty acids, coconut oil fatty acids, palm kernel oil fatty acids, peanut seed oil fatty acids, rapeseed oil fatty acids, rice bran oil fatty acids, safflower oil fatty acids, sesame oil fatty acids, soybean oil fatty acids, sunflower seed oil fatty acids, and walnut oil fatty acids. In some preferred embodiments and aspects disclosed herein, the one or more glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of glycerol-limited soybean oil fatty acids.

[0079] The one or more glycerol-limited vegetable oil fatty acids can comprise between 0 weight percent and 0.01 weight percent, or between 0 weight percent and 0.02 weight percent, or between 0 weight percent and 0.03 weight percent, or between 0 weight percent and 0.05 weight percent, or between 0.05 weight percent and 0.1 weight percent, or about 0 weight percent glycerol, based on the total weight of the one or more glycerol-limited vegetable oil fatty acids.

[0080] The one or more glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of glycerol-limited soybean oil fatty acids. The glycerol-limited soybean oil fatty acids can be hydrolyzed soybean oil refined to glycerol. While the composition of soybean oil as a natural product can vary, the composition of soybean oil tends to fall within a specific range. The glycerol-limited soybean oil fatty acids can comprise, consist of, or consist essentially of about 2 weight percent to 15 weight percent alpha-linolenic acid, about 46 weight percent to about 56 weight percent linoleic acid, about 17 weight percent to about 28 weight percent oleic acid, about 1 weight percent to about 10 weight percent stearic acid, and about 5 weight percent to about 15 weight percent palmitic acid, and / or their respective salts, based on the weight of the glycerol-limited soybean oil fatty acid. For clarity, the weight of the glycerol-limited soybean oil fatty acid includes the glycerol content, if present.

[0081] In one exemplary embodiment, glycerol-limited soybean oil fatty acids (89.6 parts by weight) are combined with tetraethylenepentamine (17.1 parts by weight) in a round-bottom flask equipped with a temperature probe, a stirrer, a nitrogen inlet, and a Dean-Stark apparatus. Heavy aromatic naphtha (HAN) (18.3 parts by weight) is added to the combination to form a mixture. A nitrogen purge is initiated, and the mixture is heated to about 170°C for about 10 hours. An amount of HAN is added to the reaction mixture to replace the amount of HAN lost in the Dean-Stark trap. The contents of the flask are stirred for an additional 10 minutes and cooled to room temperature to provide an additive composition. The additive composition comprises multiple amides and HAN. The additive can be used in a variety of applications, including as a corrosion inhibitor.

[0082] The first additive according to the first aspect of the present invention can be used in additive compositions as highly effective corrosion inhibitors, dispersants, lubricants, antifoaming agents, foaming agents, and / or release agents. In a preferred embodiment, the first additive is used in a corrosion-inhibiting composition. More preferably, such compositions are useful for corrosion protection in oil refinery facilities. In such facilities, the composition can be added to one or more process streams, whereby the presence of the additive in the streams helps protect equipment surfaces in contact with the treated process streams from corrosion. Additionally or alternatively, the composition can be used to passivate equipment surfaces prior to contacting those surfaces with treated and / or untreated process streams.

[0083] Nevertheless, a combined additive comprising, which may consist of, or consist essentially of a combination of the first reaction product described above and the second reaction product described below may be even more effective as a corrosion inhibitor, dispersant, lubricant, antifoam, foaming agent, and / or release agent. The second reaction product comprises one or more fatty acid esters, preferably glycerol-limited fatty acid esters derived from one or more vegetable oil fatty acids listed herein with respect to Scheme 9.

[0084] Second Aspect of the Invention

[0085] This embodiment illustrates how the glycerol-limited fatty acid amides described with respect to Scheme 9 can also be used in combination with glycerol-limited fatty acid esters derived from one or more vegetable oils. This combination is useful as an additive in additive compositions for a variety of purposes, such as those listed with respect to Scheme 9, and is preferably useful for corrosion protection in oil refineries or other environments where corrosion protection is desirable. Thus, in a second aspect of the present invention, there is provided a combination additive comprising, consisting of, or consisting essentially of the first and second reaction products described above. The weight ratio of the first reaction product to the second reaction product in the combined additive, respectively, or alternatively, the weight ratio of total fatty amides to total fatty esters can be selected from a wide range such as 50:1 to 1:50, or 4:1 to 1:5, or 3:1 to 1:4, or 2:1 to 1:4, or 1:1 to 1:4, or 1:2 to 1:4, or 1:3 to 1:4, or 4:1 to 1:6, or 4:1 to 1:7, or 1:1 to 1:7, or 2:1 to 1:6, or about 2:7. The first reaction product comprises a plurality of fatty acid amides, while the second reaction product comprises a plurality of fatty acid esters.

[0086] The second reaction product can be made as shown in Scheme 10, where VOFA is a glycerol-limited vegetable oil fatty acid: Scheme 10 VOFA + tertiary amine (+ optional solvent(s)) - HO ---- → Second Reaction Product (+Optional Solvent(s))

[0087] The second reaction product comprises, consists of, or consists essentially of a plurality of esters. The second reaction product is derived from a second set of reactants comprising, consisting of, or consisting essentially of a second set of one or more glycerol-limited vegetable oil fatty acids and a compound comprising at least one tertiary amine moiety and at least one hydroxyl group. The second set of one or more glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of one or more hydrolyzed vegetable oils that have been refined to glycerol.

[0088] The reaction produces a second reaction product and by-product water, as shown in Scheme 10. Preferably, at least a portion, or even most or all, of the reaction by-product water is removed during the reaction.

[0089] Preferably, by-product water is separated from the reaction mixture. Advantageously, at least a portion, or even most or all, of the by-product water can be removed during the reaction. Removal of water during the reaction helps drive the ester-forming reaction. Thus, the dried second reaction product can comprise, consist of, or essentially consist of esters and any by-products (if present). In this context, "essentially consisting of" allows for the presence of small amounts of water in the ester; even in the dry or partially dried state, the ester may contain small amounts of residual water from the reaction and / or some water absorbed from the environment. The second reaction product may comprise about 0 weight percent to 1 weight percent, or about 0 weight percent to 5 weight percent, or about 0 weight percent to 2 weight percent, or about 0 weight percent to 3 weight percent, or about 0 weight percent to 4 weight percent, or about 0.5 weight percent to 5 weight percent, or about 0.5 weight percent to 4 weight percent, or about 0.5 weight percent to 3 weight percent, or about 0.5 weight percent to 2 weight percent, or about 0.5 weight percent to 1 weight percent, or about 0 weight percent to 10 weight percent, or about 0 weight percent to about 20 weight percent, or about 0.5 weight percent to about 10 weight percent, or about 0.5 weight percent to about 20 weight percent water, based on the weight of the plurality of esters.

[0090] The second reaction product can consist of, or consist essentially of, the ester, or the second reaction product can include, consist of, or consist essentially of the ester and by-products and / or other materials. The second reaction product can comprise about 99 to 100 weight percent ester, or about 95 to 100 weight percent ester, or about 98 to 100 weight percent ester, or about 97 to 100 weight percent ester, or about 96 to 100 weight percent ester, or about 95 to 99.5 weight percent ester, or about 96 to 99.5 weight percent ester, or about 97 to 99.5 weight percent, or about 98 to 99.5 weight percent, or about 99 to 99.5 weight percent ester, or about 90 to 100 weight percent, or about 80 to about 100 weight percent, or about 90 to about 99.5 weight percent, or about 80 to about 99.5 weight percent ester, based on the weight of the second reaction product.

[0091] The second reaction product can comprise a total amount of each of the following types of individual materials: rosin acid, salts of rosin acid, amides of rosin acid, esters of rosin acid, fatty acid esters, imidazolines, and C1-C10 monohydric alcohols, based on the weight of the second reaction product, from 0 weight percent to 1 weight percent, or from 0 weight percent to 2 weight percent, or from 0 weight percent to 3 weight percent, or from 0 weight percent to 4 weight percent, or from 0 weight percent to 0.1 weight percent, or from 0 weight percent to 0.01 weight percent, or 0 weight percent.

[0092] The second set of reactants may comprise, consist of, or consist essentially of one or more glycerol-limited vegetable oil fatty acids of the second set and one or more compounds comprising one or more tertiary amine moieties and one or more hydroxyl groups (referred to herein for convenience as "tertiary amines"). The one or more tertiary amines may comprise, consist of, or consist essentially of one or more of mono-, di-, and trialkanolamines. In some preferred embodiments and aspects herein, the one or more tertiary amines may comprise, consist of, or consist essentially of triethanolamine (TEA) ((HOCHCH)N).

[0093] The second set of one or more glycerol-limited vegetable oil fatty acids may be the same, partially the same, or different from those used to make the first reaction product described with respect to Scheme 9, and may be selected from one or more of glycerol-limited avocado oil fatty acids, canola oil fatty acids, palm kernel oil fatty acids, corn oil fatty acids, cottonseed oil fatty acids, grape seed oil fatty acids, hazelnut oil fatty acids, hemp seed oil fatty acids, linseed oil fatty acids, olive oil fatty acids, coconut oil fatty acids, palm kernel oil fatty acids, peanut seed oil fatty acids, rapeseed oil fatty acids, rice bran oil fatty acids, safflower oil fatty acids, sesame oil fatty acids, soybean oil fatty acids, sunflower seed oil fatty acids, and walnut oil fatty acids.

[0094] In certain preferred embodiments and aspects disclosed herein, the second set of one or more glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of glycerol-limited soybean oil fatty acids.

[0095] The second set of glycerol-limited vegetable oil fatty acids can comprise between 0 weight percent and 0.01 weight percent, or between 0 weight percent and 0.02 weight percent, or between 0 weight percent and 0.03 weight percent, or between 0 weight percent and 0.05 weight percent, or between 0.05 weight percent and 0.1 weight percent, or about 0 weight percent glycerol, based on the weight of the second set of glycerol-limited vegetable oil fatty acids (including glycerol content, if present).

[0096] Third aspect of the invention

[0097] In a third aspect of the present invention, there is provided a concentrate comprising any of the additives of the first or second aspects of the present invention, further comprising an organic solvent, wherein the amides, their ammonium salts, and / or esters are dissolved, dispersed, or miscible with the organic solvent. The term "concentrate" is defined above in the detailed description, and that definition applies to the third aspect of the present invention and to any aspect in which one or more additives of the present invention are incorporated into a concentrate.

[0098] The organic solvent can be selected from a wide range of liquid carriers, such as esters and / or hydrocarbons. The hydrocarbon can be selected from one or more of aromatics, alkanes, any type of naphtha, and alkenes. Examples of suitable hydrocarbons include, but are not limited to, one or more of benzene, toluene, xylene (o-xylene, m-xylene, p-xylene, and any combination thereof), heavy aromatic naphtha (HAN), C5-C17 alkanes, alkenes, and naphthas. Examples of esters include, but are not limited to, phthalate esters, such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, and combinations thereof. The solvent can comprise, consist of, or consist essentially of dimethyl phthalate.

[0099] The weight ratio of the organic solvent to the first reaction product, the second reaction product, or the combination of the first and second reaction products can be 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1, or about 1:1, or 1:3 to 1:5, or 1:2 to 1:6, or about 1:4.

[0100] The weight concentration of the first reaction product, the second reaction product, or the combination of the first and second reaction products in the concentrate can be from 50 weight percent to 99 weight percent, or from 50 weight percent to 90 weight percent, or from 50 weight percent to 80 weight percent, or from 60 weight percent to 90 weight percent, or from 60 weight percent to 80 weight percent, or from 70 weight percent to 90 weight percent, or from 70 weight percent to 99 weight percent, or about 80 weight percent, based on the weight of the concentrate.

[0101] Fourth aspect of the invention

[0102] In a fourth aspect of the present invention, there is provided an additive comprising, consisting of, or consisting essentially of one or more ammonium salts of any of the glycerol-restricted amides described above in the first aspect of the present invention. The ammonium salts can be made by reacting the amide-containing components with one or more of an inorganic acid, an organic acid, an alkyl halide, and an aryl halide. The resulting ammonium salts can be incorporated into an additive composition, such as a corrosion inhibitor composition, optionally in combination with one or more glycerol-restricted amides, one or more glycerol-restricted esters described in the second aspect, optionally a solvent, optionally one or more additional optional components, and combinations thereof.

[0103] The inorganic acid may comprise, consist of, or consist essentially of hydrochloric acid. The organic acid may comprise, consist of, or consist essentially of one or more of acetic acid, acrylic acid, and methacrylic acid. The alkyl halide may comprise, consist of, or consist essentially of an alkyl chloride. The aryl halide may comprise, consist of, or consist essentially of an aryl chloride.

[0104] In an exemplary embodiment, the plurality of glycerol-limited amides comprises an amide, each amide having the structure R—(CO)—(NH)—(CHCHNH)CHCHNH, where R is a hydrocarbyl group and x is 0 to 100. The amide reacts with and is dissolved in an acid such as HY, HY, HY, and / or the like (e.g., acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, oxalic acid, maleic acid, other carboxylic acids, etc.), where each Y is independently one or more anions such that the acid at least partially dissociates in water at 25° C. and 1 atmosphere to provide an aqueous composition having a pH less than 7, or even less than 5, or even less than 4, or even less than 3; the reaction for acid HY can be represented in Scheme 11 as follows: Scheme 11 R-(CO)-(NH)-(CH2CH2NH)xCH2CH2NH2+(x+1)HY(aq)→ [R-(CO)-(NH)-(CH2CH2NH2 + )xCH2CH2NH3 + ]Y (x+1) (aq)

[0105] In general, the reaction between an acid and multiple amides can be summarized as follows: Scheme 12 Multiple amides + acids (aq) → multiple ammonium salts (aq)

[0106] Similarly, one or more of the amine groups of the amides can be converted to an alkyl or aryl ammonium group.

[0107] In a purely exemplary embodiment, the amides are represented by the structure R 1 -(CO)-(NH)-(CHCHNH)CHCHNH, wherein R 1 is a hydrocarbyl group and x is 0 to 100. Amides are groups of the formula R 2 By reacting with an alkyl halide, such as an alkyl halide bearing X, one or more of the amine groups on the amide are converted to an ammonium salt, and R 2 is a hydrocarbyl group containing 1 to 50 carbon atoms and X is a halide such as Cl and / or F. In a purely exemplary scheme, all or a portion of the amino-NH groups are converted to quaternary ammonium groups: Scheme 13 R-(CO)-(NH)-(CH2CH2NH)xCH2CH2NH2+(2x+3)R 2 Cl(aq) → [R—(CO)—(NH)—(CH2CH2NR 2 2 + )xCH2CH2NR 2 3 + ]Cl (x+1) (aq)+(x+2)HCl

[0108] In general, the reaction between a hydrocarbyl halide and multiple amides can be summarized as follows: Scheme 14 Multiple amides + hydrocarbyl halides → multiple hydrocarbyl ammonium salts

[0109] The ammonium salts disclosed herein are particularly useful as additives to aqueous process streams, e.g., as aqueous corrosion inhibitors, while additives comprising, consisting of, or consisting essentially of amides are particularly useful as corrosion inhibitor additives to, for example, hydrocarbon process streams.

[0110] Any of the additives and concentrates or other compositions of the first, second, third, or fourth aspects of the present invention may include one or more optional ingredients, such as one or more polymerization inhibitors, antioxidants, and amines, or other optional ingredients as discussed in other schemes described herein.

[0111] Fifth aspect of the invention

[0112] In a fifth aspect of the present invention, there is provided a method for making the first additive described above with respect to Schemes 4a, 4b, and 9. The method includes (1) combining one or more glycerol-limited vegetable oil fatty acids with a polyamine to form a reaction mixture. The one or more glycerol-limited vegetable oil fatty acids may comprise, consist of, or consist essentially of one or more hydrolyzed vegetable oils at least partially refined to glycerol. Optionally, the method further includes (2) adding a hydrocarbon solvent, such as heavy aromatic naphtha (HAN), to the reaction mixture as a liquid carrier. Preferably, the hydrocarbon solvent has a boiling point of at least 160° C. at 1 atmosphere. However, the reaction may be carried out at pressures greater than 1 atmosphere to increase the boiling point of the hydrocarbon solvent and achieve the desired reaction temperature.

[0113] The molar ratio of one or more glycerol-limited vegetable oil fatty acids to polyamine in the combined reaction mixture can be 3:1 to 4:1, or 3.4:1 to 3.7:1, or about 3.5:1 to 3.6:1. While the glycerol-limited vegetable oil fatty acid or fatty acids can be a complex mixture of fatty acids, the acid value of the free fatty acid can be used to calculate the molecular weight of the free fatty acid to calculate the aforementioned molar ratio. If the polyamine is a mixture of individual polyamine compounds with varying molecular weights, the number-average molecular weight of the polyamine can be used to calculate the aforementioned molar ratio. However, if the polyamine is a discrete compound, such as tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2), the molecular weight of the discrete compound is used.

[0114] The method further includes (3) heating the reaction mixture, optionally under an inert gas such as nitrogen, argon, at a suitable reaction temperature, such as a temperature ranging from 150°C to 200°C, or 160°C to 190°C, or 160°C to 175°C, or 165°C to 170°C, for a period ranging from 30 minutes to 20 hours, or 1 hour to 15 hours, or 1 hour to 10 hours, or 5 hours to 15 hours, to form a first reaction product and by-product water. Preferably, a reaction temperature of 200°C is not exceeded to avoid the formation of excessive amounts of imidazoline as a by-product.

[0115] Preferably, the method further comprises (4) removing by-product water from the reaction mixture during heating, for example, by trapping the water in a Dean-Stark trap during heating. Removing water while heating the reaction aids in driving the reaction to produce the desired amide.

[0116] Sixth aspect of the invention

[0117] A sixth aspect of the present invention provides a method for making the combined additive described above in the second aspect of the present invention. The method includes (1) optionally, but preferably, combining one or more first glycerol-limited vegetable oil fatty acids with a polyamine to form a first reaction mixture under conditions such that the temperature of the reaction mixture does not exceed 100°C. The glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of one or more hydrolyzed vegetable oils at least partially refined to glycerol. The one or more glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of glycerol-limited soybean oil fatty acids. The polyamine can comprise, consist of, or consist essentially of tetraethylenepentamine (HNCHCHNHCHCHNHCHCHNHCHCHNHCHCHNH) (TEPA). Optionally, the method further includes (2) adding a hydrocarbon solvent, such as heavy aromatic naphtha (HAN), to the reaction mixture. Preferably, the hydrocarbon solvent has a boiling point of at least 160° C. at 1 atmosphere. However, the reaction may be carried out at pressures greater than 1 atmosphere to increase the boiling point of the hydrocarbon solvent and achieve the desired reaction temperature.

[0118] The molar ratio of total glycerol-limited vegetable oil fatty acids to total polyamines in the reaction mixture can be 3:1 to 4:1, or 3.4:1 to 3.7:1, or about 3.5:1 to 3.6:1. The glycerol-limited vegetable oil fatty acids or fatty acids can be a mixture of fatty acids, and the acid value of the free fatty acids can be used to calculate the molecular weight of the free fatty acids to calculate the aforementioned molar ratios. If the polyamine is a mixture of individual polyamine compounds with varying molecular weights, the number-average molecular weight of the polyamine can be used to calculate the aforementioned molar ratios. However, if the polyamine is a discrete compound, such as tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2), the molecular weight of the discrete compound is used.

[0119] The method further includes (3) heating the reaction mixture, optionally under an inert gas such as nitrogen or argon, at a reaction temperature ranging from 150°C to 200°C, or 160°C to 190°C, or 160°C to 175°C, or 165°C to 170°C, for a period ranging from 30 minutes to 20 hours, or 1 hour to 15 hours, or 1 hour to 10 hours, or 5 hours to 15 hours, to form a first reaction product comprising water and the first additive. Preferably, a reaction temperature of 200°C is not exceeded to avoid formation of excessive amounts of imidazoline as a by-product.

[0120] Preferably, the method further comprises (4) removing water from the reaction mixture during heating, for example, by trapping water in a Dean-Stark trap during heating.

[0121] The method further includes (5) combining the second one or more glycerol-limited vegetable oil fatty acids with one or more tertiary amines to form a second reaction mixture, wherein each of the one or more tertiary amines comprises at least one hydroxyl group; and (6) heating the second reaction mixture, optionally under an inert gas such as nitrogen, at a reaction temperature ranging from 150° C. to 300° C., or 160° C. to 275° C., or 170° C. to 250° C., or 180° C. to 230° C., or 190° C. to 220° C., or 200° C. to 220° C., or about 210° C., for a period ranging from 30 minutes to 10 hours, or 1 hour to 10 hours, or 2 hours to 10 hours, or 3 hours to 10 hours, or 3 hours to 7 hours, or 3 hours to 6 hours, or 3 hours to 5 hours, or about 4 hours, to form a second reaction product and by-product water.

[0122] The second one or more glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of a hydrolyzed vegetable oil at least partially refined to glycerol as described herein. The second one or more glycerol-limited vegetable oil fatty acids can comprise, consist of, or consist essentially of a glycerol-limited soybean oil fatty acid. The one or more tertiary amines can comprise, consist of, or consist essentially of triethanolamine.

[0123] The molar ratio of the second one or more glycerol-limited vegetable oil fatty acids to the one or more tertiary amines in the second reaction mixture may be selected from a wide range, such as from 1:1 to 2:1, or from 1.5:1 to 1.7:1, or about 1.6:1. Although the glycerol-limited vegetable oil fatty acid or acids comprise a mixture of fatty acids, the acid value of the one or more glycerol-limited vegetable oil fatty acids may be used to calculate the molecular weight in order to calculate the aforementioned molar ratios.

[0124] Optionally, the method of making the combined additive further comprises (7) adding a hydrocarbon solvent, such as heavy aromatic naphtha (HAN), to the second reaction mixture before, after, or during the heating thereof.

[0125] Preferably, the method further comprises (8) removing water from the second reaction mixture during heating, for example, by trapping water in a Dean-Stark trap during heating.

[0126] The method of making the additive combination further includes combining the first reaction product and the second reaction product to form the additive combination. The weight ratio of the total amide content to the total ester content in the additive combination can be selected from a wide range, such as 50:1 to 1:50, 4:1 to 1:5, 3:1 to 1:4, 2:1 to 1:4, 1:1 to 1:4, 1:2 to 1:4, 1:3 to 1:4, 4:1 to 1:6, 4:1 to 1:7, 1:1 to 1:7, 2:1 to 1:6, or about 2:7.

[0127] Any of the first additives, second additives, and / or combined additives disclosed herein can be added to a hydrocarbon composition containing one or more hydrocarbons to provide a treated hydrocarbon composition.

[0128] Seventh aspect of the invention

[0129] Accordingly, in a seventh aspect of the present invention, there is provided a method of inhibiting corrosion of a surface in contact with a hydrocarbon composition, the method comprising, consisting of, or consisting essentially of combining the hydrocarbon composition with any one or more of the first additive composition, second additive composition, and / or combined additive composition disclosed herein.

[0130] The surface may comprise, consist of, or consist essentially of one or more of iron, copper, nickel, molybdenum, cobalt, carbon steel, chromium, stainless steel, and low alloy steel.

[0131] The additives may be added to a batch or process stream of the hydrocarbon composition in a wide range of amounts, such as 1 to 24 parts by weight of one or more additives per million parts by weight (ppm) of the hydrocarbon composition, or 2 to 9 ppm, or 0.1 to 1000 ppm, or 0.5 to 100 ppm, or 0.5 to 50 ppm, or 0.1 to 10,000 ppm by weight of one or more additives.

[0132] The hydrocarbon composition may be a process stream comprising, consisting of, or consisting essentially of one or more hydrocarbons; or a batch of hydrocarbon compositions comprising, consisting of, or consisting essentially of one or more hydrocarbons. The hydrocarbon composition may comprise, consist of, or consist essentially of one or more of crude oil, refined petroleum, cracked petroleum, hydrotreating process streams, liquid ethylene, liquid methane, and naphtha.

[0133] The additive compositions comprising multiple amides, the additive compositions comprising multiple esters, and the combined additive compositions described herein can be added to hydrocarbon compositions to provide protection against corrosion of surfaces, such as carbon steel surfaces, that come into contact with the hydrocarbon composition and / or hydrocarbon process stream. A common corrosive in hydrocarbon compositions derived from crude oil is naphthenic acid and / or its salts. Thus, in any of the embodiments described herein, the hydrocarbon composition or process stream may include naphthenic acid. The additives in the additive compositions provide corrosion protection, but may also provide protection against deposits and / or sediments by acting as dispersants.

[0134] The hydrocarbon composition may contain one or more corrosive substances selected from one or more of naphthenic acid and / or its salts, water, brine, organic chlorides, inorganic chlorides, hydrogen sulfide, organic sulfur compounds, carbon dioxide, dissolved oxygen gas, organic acids, sodium chloride, magnesium chloride, calcium chloride, and inorganic ammonium chloride (NH4Cl). The organic sulfur compounds may include mercaptans such as one or more of methyl mercaptan, ethyl mercaptan, and propyl mercaptan. A hydrocarbon composition containing any one or more corrosive substances in contact with metal parts and / or contaminants may cause corrosion thereof. The addition of the additives disclosed herein inhibits such corrosion. In other words, when the disclosed additives are added to a hydrocarbon composition containing one or more corrosive substances, corrosion of surfaces, such as carbon steel surfaces, in contact with the treated process stream appears to be delayed. Without being limited by theory, the inventors speculate that the additives modify, either temporarily or permanently, metal surfaces in contact with or contacted by the additive. Alternatively, the additive may somehow inhibit the effects of corrosive substances in the oil. Regardless of the mechanism, the additive provides corrosion protection when added to a hydrocarbon composition in contact with corroding metal parts.

[0135] Any of the additives, reaction products, amides, and esters described herein can be used in compositions and methods in downstream oil processes, for example, in the manner described in U.S. Pat. No. 3,766,053, the entirety of which is incorporated herein by reference for all purposes.

[0136] Eighth aspect of the present invention

[0137] Thus, in an eighth aspect of the present invention, there is provided a processed hydrocarbon composition comprising, consisting of, or consisting essentially of any of the hydrocarbon compositions disclosed herein, as well as any one or more of the additive compositions, reaction products, amides, esters, and combinations thereof described herein. Prior to the addition of the additive, the hydrocarbon composition comprises, consists of, or consists essentially of one or more hydrocarbons.

[0138] The ratio of the weight of the additive composition, reaction product, amides, esters, and combinations thereof to the weight of the treated hydrocarbon composition can be from 1 to 24 parts per million (ppm) by weight, or from 2 to 9 ppm, or from 0.1 to 1000 ppm, or from 0.5 to 100 ppm, or from 0.5 to 50 ppm, or from 0.1 to 10000 ppm by weight.

[0139] Any of the additive compositions, reaction products, amides, esters, and combinations thereof described herein may comprise from 0 weight percent to 5 weight percent glycerol, or from 0 weight percent to 4 weight percent, or from 0 weight percent to 3 weight percent, or from 0 weight percent to 2 weight percent, or from 0 weight percent to 1 weight percent, or from 0 weight percent to 0.1 weight percent, or from 0 weight percent to 0.01 weight percent, or from 0 weight percent, or from 0.0001 weight percent to 0.1 weight percent glycerol, respectively, based on the weight of the additive composition, reaction product, amides, esters, and combinations thereof.

[0140] Any of the additive compositions, reaction products, amides, esters, and combinations thereof described herein may each comprise from 0 weight percent to 4 weight percent, or from 0 weight percent to 3 weight percent, or from 0 weight percent to 2 weight percent, or from 0 weight percent to 1 weight percent, or from 0 weight percent to 0.1 weight percent, or from 0 weight percent to 0.01 weight percent, or from 0 weight percent, or from 0.0001 weight percent to 0.1 weight percent of total rosin, total resin acid, total resin acid derivatives, or any combination thereof, based on the weight of the additive composition, reaction product, amides, esters, and combinations thereof, respectively. [Example]

[0141] The following examples are intended to illustrate different aspects and embodiments of the present invention and should not be considered as limiting the scope of the invention, it will be appreciated that various modifications and variations can be made without departing from the scope of the claims.

[0142] Example 1: Synthesis of SOFA-TEPA Amide from Glycerol-Limited Soybean Oil Fatty Acids Obtained from Supplier A

[0143] Glycerol-limited soybean oil fatty acids (89.6 g) obtained from a first supplier, Supplier A, was added to a 250 mL four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. Tetraethylenepentamine (17.1 g, 0.090 mol) was then charged to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to increase from 21°C to approximately 44°C. Heavy aromatic naphtha (18.3 g) was then charged to the well-stirred reaction mixture. A nitrogen purge was initiated, and the reaction was heated to approximately 170°C and held for approximately 10 hours. The reaction was cooled to below 100°C, and an amount of heavy aromatic naphtha (HAN) equal to the volume of liquid collected in the Dean-Stark trap was added to the flask. The contents of the flask were stirred for an additional 10 minutes and allowed to cool to room temperature. The product remained a clear liquid and showed no signs of phase separation over time.

[0144] Example 2: Synthesis of SOFA-TEPA Amide from Glycerol-Limited Soybean Oil Fatty Acids Obtained from Supplier B

[0145] Glycerol-limited soybean oil fatty acids (72.73 g) obtained from a second supplier, Supplier B, were added to a 250 mL four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. Tetraethylenepentamine (13.68 g, 0.072 moles) was then charged to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to increase from 21°C to approximately 61°C. Heavy aromatic naphtha (HAN) (13.59 g) was then charged to the well-stirred reaction mixture. A nitrogen purge was initiated, and the reaction was heated to approximately 170°C and held for approximately 10 hours. The reaction was cooled to below 100°C, and an amount of heavy aromatic naphtha (HAN) equal to the volume of liquid collected in the Dean-Stark trap was added to the flask. The contents of the flask were stirred for an additional 10 minutes and allowed to cool to room temperature. The product remained a clear liquid and showed no signs of phase separation over time.

[0146] Example 3: Synthesis of SOFA-TEA esters from glycerol-limited soybean oil fatty acids obtained from Supplier A

[0147] Glycerol-limited soybean oil fatty acids (44.97 g) obtained from Supplier A were added to a 250 mL, four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. Triethanolamine (15.75 g, 0.10 mol) was then charged to the well-stirred reaction mixture. The reaction was heated to approximately 210°C and held at that temperature for approximately 4 hours. The reaction was cooled to below 100°C, and heavy aromatic naphtha (39.28 g) was added to the flask. The contents of the flask were stirred for an additional 10 minutes and allowed to cool to room temperature. The product remained a clear liquid and showed no signs of phase separation over time.

[0148] Example 4: Synthesis of SOFA-TEA esters from glycerol-limited soybean oil fatty acids obtained from Supplier B

[0149] Glycerol-limited soybean oil fatty acids (45.65 g) obtained from Supplier B were added to a 250 mL, four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. Triethanolamine (15.75 g, 0.10 mol) was then charged to the well-stirred reaction mixture. The reaction was heated to approximately 210°C and held at that temperature for approximately 4 hours. The reaction was cooled to below 100°C, and heavy aromatic naphtha (38.60 g) was added to the flask. The contents of the flask were stirred for an additional 10 minutes and allowed to cool to room temperature. The product remained a clear liquid and showed no signs of phase separation over time.

[0150] Example 5: Additives from soybean oil

[0151] To a 1-liter, four-necked, round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar, 343.5 g of soybean oil was added along with a few drops (0.01 g) of antifoam silicone. The flask and its contents were heated to 80° C. under a nitrogen purge, and diethylenetetramine (129.99 g, 1.26 moles) was added slowly so that the contents of the flask did not exceed 100° C. and to avoid foaming. After the addition was complete, the contents of the flask were heated to 165° C. for 1 hour to form the amide, and a small sample was removed and measured at 1742 cm. -1 The disappearance of the peak associated with the ester carbonyl at 1645 cm -1 The reaction mixtures were monitored for the formation of amides by examining the samples by infrared spectroscopy for the appearance of a peak associated with the amide carbonyl at .

[0152] The contents of the reaction flask were then heated to 245°C for 3 hours to cyclize the amide to the imidazoline. A small sample was removed and the reaction mixture was analyzed at 1645cm -1 Disappearance of the amide carbonyl peak at 1602 cm -1 The reaction was monitored for the formation of the imidazoline by examining the samples by infrared spectroscopy for the appearance of an imine peak at .

[0153] The contents of the reaction vessel were cooled and transferred to a jar. Immediately after transfer, the contents of the jar were a clear liquid, but after 3 days, the contents of the jar were cloudy and had separated into layers.

[0154] Example 6: Additives from glycerol-limited soybean oil fatty acids

[0155] Glycerol-limited soybean oil fatty acids (70.99 g) were added to a 250 mL four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. 2-Aminoethylethanolamine (29.00 g, 0.278 mol) was then charged to the well-stirred reaction mixture. The temperature of the contents of the flask was increased from room temperature to about 50 to about 60°C. The viscous reaction mass was heated to about 180°C for about 8 hours. The reaction mixture was then heated to about 225°C and held at that temperature for about 5 hours. Approximately 4 to 5 mL of water was collected in the Dean-Stark trap. The contents of the flask were cooled to below 100°C and transferred to a jar.

[0156] A sample of the reaction product, SOFA-imidazoline, was stored at -10°C and exhibited no turbidity or precipitation after 11 days and 3 months.

[0157] A sample of the SOFA-imidazoline product (8 g) was blended with dimethyl phthalate (2 g) to form a concentrate. The concentrate was stored at −10° C. and showed no turbidity or precipitation after 1 week, 44 days, or even 95 days.

[0158] Example 7: Additive concentrate from tall oil fatty acids

[0159] The procedure of Example 6 was repeated except that tall oil fatty acids were used instead of the glycerol-limited soybean oil fatty acids.

[0160] A sample of the reaction product, TOFA imidazoline, was stored at -10°C for 11 days and exhibited a precipitate.

[0161] A sample of the TOFA-imidazoline product (8 g) was blended with dimethyl phthalate (2 g) to form a concentrate. The concentrate was stored at −10° C. and exhibited a precipitate after only a few days. After 64 days of storage at −10° C., the precipitate could not be easily redissolved.

[0162] Comparison with Example 6 shows that the SOFA-imidazoline additive, both in 100% form and when formulated as a concentrate in organic solvent (dimethyl phthalate), was more stable than the corresponding TOFA-imidazoline additive when stored at low temperatures.

[0163] Example 9: Synthesis of TOFA-TEPA amide from tall oil fatty acid

[0164] The synthesis procedures of Examples 1 and 2 were repeated except that the glycerol-limited soybean oil fatty acids were replaced with tall oil fatty acids.

[0165] Example 10: Synthesis of TOFA-TEA esters from tall oil fatty acids

[0166] The synthetic procedures of Examples 3 and 4 were repeated except that the glycerol-limited soybean oil fatty acids were replaced with tall oil fatty acids.

[0167] Example 11: Combination amide-ester (CAE) corrosion inhibitors

[0168] TOFA-TEPA amide and TOFA-TEA ester, prepared as in Examples 9 and 10, respectively, were mixed in a ratio of 1 part by weight of TOFA-TEPA amide to 3.5 parts by weight of TOFA-TEA ester to produce CAE2.

[0169] SOFA-TEPA amide and SOFA-TEPA ester, prepared as in Examples 2 and 4, respectively, were mixed in a ratio of 1 part by weight of SOFA-TEPA amide to 3.5 parts by weight of SOFA-TEA ester to produce CAE3.

[0170] The SOFA-TEPA amide and SOFA-TEPA ester prepared as in Examples 2 and 4, respectively, were mixed in a ratio of 1 part by weight of SOFA-TEPA amide to 3.5 parts by weight of SOFA-TEA ester to produce CAE4.

[0171] The SOFA-TEPA amide and SOFA-TEPA ester prepared as in Examples 1 and 3, respectively, were mixed in a ratio of 1 part by weight of SOFA-TEPA amide to 3.5 parts by weight of SOFA-TEA ester to produce CAE5.

[0172] Example 12: Corrosion inhibitor performance by wheelbox testing

[0173] A wheelbox test (NACE 1D182, "Wheel Test Method Used for Evaluation of Film-Persistent Corrosion Inhibitors for Oil Field Applications") was conducted to evaluate three different concentrations of each of CAE2 through CAE5 in hydrotreated light distillates as oil. An additional sample of crude oil without any of the combined amide-ester corrosion inhibitors, labeled CAE1, was also evaluated, as shown in Table 1. Several samples of each of CAE2 through CAE5 were evaluated.

[0174] Wheelbox tests were conducted using brine (49.7 grams of NH4Cl per liter and 9.9 grams of HCl per liter in water), the gas was saturated HS, the coupons were 1 / 4 inch by 7 3 / 8 inch 1018 mild steel with a sandblasted finish, the wheel rotation speed was 26 revolutions per minute (RPM), the test temperature was 160°F (71°C), and the test time was 24 hours. Corrosion inhibition results are also presented in Table 1.

[0175] [Table 1]

[0176] Excellent corrosion protection results were obtained with corrosion inhibitors CAE2, CAE3, CAE4, and CAE5.

Claims

1. an additive composition comprising a plurality of amides and / or ammonium salts thereof, wherein at least a portion of the plurality of amides comprises a reaction product derived from a first set of reactants comprising a first one or more glycerol-limited vegetable oil fatty acids and a polyamine; the first one or more glycerol-limited vegetable oil fatty acids comprise from 0 weight percent to 0.1 weight percent glycerol, based on the weight of the first one or more glycerol-limited vegetable oil fatty acids; The polyamine has the formula NH ２ (CH ２ CH ２ NH)xCH ２ CH ２ NH ２ wherein x is 0 to 100.

2. 2. The additive composition of claim 1, wherein x is 0 to 10.

3. 3. The additive composition of claim 1 or 2, wherein the first one or more glycerol-limited vegetable oil fatty acids comprise glycerol-limited soybean oil fatty acids.

4. the additive composition further comprises a plurality of esters, at least a portion of the plurality of esters comprising a second reaction product derived from a second set of reactants comprising a second one or more glycerol-limited vegetable oil fatty acids and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxyl group; 3. The additive composition of claim 1 or 2, wherein the second one or more glycerol-limited vegetable oil fatty acids comprise from 0 weight percent to 0.1 weight percent glycerol, based on the weight of the second one or more glycerol-limited vegetable oil fatty acids.

5. 5. The additive composition of claim 4, wherein the one or more tertiary amines comprise triethanolamine.

6. 5. The additive composition of claim 4, wherein the second one or more glycerol-limited vegetable oil fatty acids comprise glycerol-limited soybean oil fatty acids.

7. 3. The additive composition of claim 1, wherein the one or more first glycerol-limited vegetable oil fatty acids and the second one or more glycerol-limited vegetable oil fatty acids consist of glycerol-limited soybean oil fatty acids.

8. 3. The additive composition of claim 1 or 2, wherein the additive composition comprises 0 to 0.1 weight percent of glycerol based on the weight of the additive composition.

9. The polyamine is tetraethylenepentamine (H ２ NCH ２ CH ２ NHCH ２ CH ２ NHCH ２ CH ２ NHCH ２ CH ２ NH ２ 3. The additive composition of claim 1 or 2, comprising:

10. 3. The additive composition of claim 1 or 2, wherein each of the first one or more glycerol-limited vegetable oil fatty acids and the second one or more glycerol-limited vegetable oil fatty acids independently comprises from about 2 weight percent to about 15 weight percent alpha-linolenic acid, from about 46 weight percent to about 56 weight percent linoleic acid, from about 17 weight percent to about 28 weight percent oleic acid, from about 1 weight percent to about 10 weight percent stearic acid, and from about 5 weight percent to about 15 weight percent palmitic acid, relative to the first one or more glycerol-limited vegetable oil fatty acids and the second one or more glycerol-limited vegetable oil fatty acids, respectively.

11. 3. The additive composition of claim 1 or 2, wherein the additive composition comprises 0 to 5 weight percent total imidazoline content, 0 to 5% rosin acid, 0 to 5 weight percent total rosin acid derivatives, 0 to 5 weight percent total C1-C10 monohydric alcohols, and 0 to 5 weight percent total fatty acid ester content based on the additive composition.

12. 3. The additive composition of claim 1 or 2, wherein the additive composition comprises the plurality of amides and heavy aromatic naphtha.

13. 1. An aqueous composition comprising: (i) the additive composition of claim 1 or 2, wherein the additive composition comprises the ammonium salts of the plurality of amides; and (ii) greater than 5 weight percent water relative to the additive composition.

14. the ammonium salts of the plurality of amides are (a) the plurality of amides; 14. The aqueous composition of claim 13, comprising at least a portion of a reaction product derived from a reactant comprising: (b) one or more of an acid, an alkyl halide, and an aryl halide.

15. 1. A hydrocarbon composition comprising: (a) one or more hydrocarbons; (b) an additive composition selected from one or more of an amide composition and an ester composition; the amide composition comprises a plurality of amides, at least a portion of the plurality of amides comprising a reaction product derived from a first set of reactants comprising a first one or more glycerol-limited vegetable oil fatty acids and a polyamine; the first one or more glycerol-limited vegetable oil fatty acids comprise from 0 weight percent to 0.1 weight percent glycerol, based on the weight of the first one or more glycerol-limited vegetable oil fatty acids; The polyamine has the formula NH ２ (CH ２ CH ２ NH)xCH ２ CH ２ NH ２ wherein x is 0 to 100; the ester composition comprises a plurality of esters, at least a portion of the plurality of esters comprising a reaction product derived from a second set of reactants comprising a second one or more glycerol-limited vegetable oil fatty acids and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxyl group; A hydrocarbon composition wherein the second one or more glycerol-limited vegetable oil fatty acids comprise from 0 weight percent to 0.1 weight percent glycerol, based on the weight of the second one or more glycerol-limited vegetable oil fatty acids.

16. 16. The hydrocarbon composition of claim 15, wherein the first one or more glycerol-limited vegetable oil fatty acids, the second one or more glycerol-limited vegetable oil fatty acids, or both the first one or more glycerol-limited vegetable oil fatty acids and the second one or more glycerol-limited vegetable oil fatty acids comprise glycerol-limited soybean oil fatty acids.

17. 17. The hydrocarbon composition of claim 15 or 16, wherein the first one or more glycerol-limited vegetable oil fatty acids, the second one or more glycerol-limited vegetable oil fatty acids, or both the first one or more glycerol-limited vegetable oil fatty acids and the second one or more glycerol-limited vegetable oil fatty acids, independently, further comprise one or more additional fatty acids.

18. 17. The hydrocarbon composition of claim 15 or 16, wherein the hydrocarbon composition comprises less than 0.1 weight percent rosin.

19. 17. The hydrocarbon composition of claim 15 or 16, wherein the hydrocarbon composition comprises from 0 to 0.1 weight percent glycerol based on the hydrocarbon composition.

20. 17. The hydrocarbon composition of claim 15 or 16, wherein the first one or more glycerol-limited vegetable oil fatty acids and the second one or more glycerol-limited vegetable oil fatty acids each comprise from about 2 weight percent to about 15 weight percent alpha-linolenic acid, from about 46 weight percent to about 56 weight percent linoleic acid, from about 17 weight percent to about 28 weight percent oleic acid, from about 1 weight percent to about 10 weight percent stearic acid, and from about 5 weight percent to about 15 weight percent palmitic acid, based on the weight of the first one or more glycerol-limited vegetable oil fatty acids and the second one or more glycerol-limited vegetable oil fatty acids, respectively.

21. The polyamine is tetraethylenepentamine (H ２ NCH ２ CH ２ NHCH ２ CH ２ NHCH ２ CH ２ NHCH ２ CH ２ NH ２ 17. The hydrocarbon composition of claim 15 or 16, comprising:

22. 17. The hydrocarbon composition of claim 15 or 16, wherein the additive composition comprises the ester composition and the one or more tertiary amines comprise triethanolamine.

23. 17. The hydrocarbon composition of claim 15 or 16, wherein the one or more hydrocarbons comprise crude oil, refined oil, cracked oil, or any combination thereof.

24. 17. The hydrocarbon composition of claim 15 or 16, wherein the one or more hydrocarbons comprise a hydrotreating process stream, liquid ethylene, liquid methane, naphtha, or any combination thereof.

25. 17. The hydrocarbon composition of claim 15 or 16, wherein the one or more hydrocarbons comprise one or more corrosive materials selected from one or more of organic chlorides, inorganic chlorides, hydrogen sulfide, organic sulfur compounds, carbon dioxide, dissolved oxygen gas, organic acids, sodium chloride, magnesium chloride, calcium chloride, and inorganic ammonium chloride.

26. 17. The hydrocarbon composition of claim 15 or 16, wherein the one or more hydrocarbons comprise naphthenic acids.

27. 17. The hydrocarbon composition of claim 15 or 16, wherein the hydrocarbon composition comprises the ester composition, the ester composition comprising one or more of one or more monoesters of triethanolamine, one or more diesters of triethanolamine, and one or more triesters of triethanolamine.

28. 17. The hydrocarbon composition of claim 15 or 16, wherein the additive composition comprises, based on the weight of the additive composition, 0 weight percent to 5 weight percent total imidazoline content, 0 weight percent to 5 weight percent rosin acid, 0 weight percent to 5 weight percent total rosin acid derivatives, 0 weight percent to 5 weight percent total C1-C10 monohydric alcohols, and 0 weight percent to 5 weight percent total fatty acid ester content.

29. 17. The hydrocarbon composition of claim 15 or 16, wherein the hydrocarbon composition comprises both the amide composition and the ester composition.

30. 17. The hydrocarbon composition of claim 15 or 16, wherein the hydrocarbon composition comprises 1 to 24 parts by weight of the additive composition per million parts by weight of the one or more hydrocarbons.

31. 17. The hydrocarbon composition of claim 15 or 16, wherein the hydrocarbon composition comprises 2 to 9 parts by weight of the additive composition per million parts by weight of the one or more hydrocarbons.

32. 10. A method for inhibiting corrosion of a surface in contact with one or more hydrocarbons, said method comprising combining an inhibitor composition with said one or more hydrocarbons, said inhibitor composition comprising the additive composition of claim 1 or 2.

33. 33. The method of claim 32, wherein 1 to 24 parts by weight of said additive composition per million parts by weight of said one or more hydrocarbons are combined.

34. 33. The method of claim 32, wherein the one or more hydrocarbons comprise crude oil, refined oil, cracked oil, or any combination thereof.

35. 33. The method of claim 32, wherein the one or more hydrocarbons comprise a hydrotreating process stream, liquid ethylene, liquid methane, naphtha, or any combination thereof.

36. 33. The method of claim 32, wherein the one or more hydrocarbons comprise naphthenic acids.

37. 33. The method of claim 32, wherein the one or more hydrocarbons comprise one or more corrosive materials selected from one or more of organic chlorides, inorganic chlorides, hydrogen sulfide, organic sulfur compounds, carbon dioxide, dissolved oxygen gas, organic acids, sodium chloride, magnesium chloride, calcium chloride, and inorganic ammonium chloride.

38. 33. The method of claim 32, wherein the inhibitor composition is combined with the one or more hydrocarbons in an ethylene plant, a cracked gas plant, a dilution stream feed pump, a cracked gas compressor, a reboiler, or a process water stripper.

39. 33. The method of claim 32, wherein the inhibitor composition further comprises one or more of a polymerization inhibitor, an antioxidant, an amine, and any combination thereof.

40. 1. A method of making an additive composition, the method comprising: (1) combining a first one or more glycerol-limited vegetable oil fatty acids with a polyamine to form a first reaction mixture, wherein the first one or more glycerol-limited vegetable oil fatty acids comprise 0 to 0.1 weight percent glycerol, based on the weight of the first one or more glycerol-limited vegetable oil fatty acids; (2) optionally adding a hydrocarbon solvent to the first reaction mixture; (3) heating the first reaction mixture at a reaction temperature of 150° C. to 200° C. for a period of 30 minutes to 20 hours to form water and a first reaction product, wherein the first reaction product comprises a plurality of amides.

41. 41. The method of claim 40, wherein the method comprises removing water from the first reaction mixture during the heating.

42. 42. The method of claim 40 or 41, wherein the method comprises adding heavy aromatic naphtha to the first reaction mixture.

43. 42. The method of claim 40 or 41, wherein the hydrocarbon solvent has a boiling point of at least 160°C at 1 atmosphere.

44. 42. The method of claim 40 or 41, wherein the reaction mixture is heated under nitrogen.

45. 42. The method of claim 40 or 41, wherein the temperature of the first reaction mixture and the temperature of the first reaction product do not exceed 200°C.

46. 42. The method of claim 40 or 41, wherein the temperature of the reaction mixture does not exceed 100°C during said combining.

47. The first one or more glycerol-limited vegetable oil fatty acids include glycerol-limited soybean oil fatty acids, and the polyamine is tetraethylenepentamine (H ２ NCH ２ CH ２ NHCH ２ CH ２ NHCH ２ CH ２ NHCH ２ CH ２ NH ２ 42. The method of claim 40 or 41, comprising:

48. 42. A method of making a combination additive composition, said method comprising the method of claim 40 or 41, (4) combining a second one or more glycerol-limited vegetable oil fatty acids with one or more tertiary amines to form a second reaction mixture; the second one or more glycerol-limited vegetable oil fatty acids comprising 0 percent to 0.1 percent glycerol by weight, based on the weight of the second one or more glycerol-limited vegetable oil fatty acids; forming a second reaction mixture, wherein each of the one or more tertiary amines comprises at least one hydroxyl group; (5) heating the second reaction mixture at a reaction temperature of 150° C. to 300° C. for a period of 30 minutes to 10 hours to form water and a second reaction product, the second reaction product comprising a plurality of esters; and (6) combining components comprising said first reaction product and said second reaction product to form said combined additive composition.

49. 49. The method of claim 48, wherein the second one or more glycerol-limited vegetable oil fatty acids comprise glycerol-limited soybean oil fatty acids and the one or more tertiary amines comprise triethanolamine.

50. 49. The method of claim 48, wherein the second reaction mixture is heated under an inert gas.

51. 49. The method of claim 48, wherein a hydrocarbon solvent is added to the second reaction mixture before the heating of the second reaction mixture, after the heating of the second reaction mixture, during the heating of the second reaction mixture, or any combination thereof.

52. 49. The method of claim 48, wherein the method comprises removing water from the second reaction mixture during the heating thereof.

53. 49. The method of claim 48, wherein the weight ratio of said amides to said esters in said combined additive composition is from 1:3 to 1:4.