Corrosion inhibiting additives and methods of making and using same

Abstract

Additives and methods of making and using these additives are described. These additives can be provided as concentrates for addition to one or more hydrocarbons in crude oil refining and processing facilities to inhibit corrosion of corrodible metal parts in contact with process streams. The additives may be prepared by reacting a glycerol-restricted vegetable oil fatty acid with an amine, wherein the glycerol-restricted vegetable oil fatty acid may be a hydrolyzed vegetable oil that is at least partially purified relative to glycerol. The additives may be further reacted to provide ammonium salts, which may be added to aqueous compositions to provide corrosion protection of erodible surfaces in contact with the aqueous compositions.

Description

Technical Field

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

[0002] In 1861, early oil refining converted crude oil into kerosene. Nowadays, refining processes generally include processing and / or treating crude oil to provide not only kerosene, but also a wide range of other products and product intermediates. Although certain process steps such as distillation, cracking, and removal of impurities and by-products are common, the techniques applicable to the same process can vary significantly among different refineries. Petroleum refining can start with the desalting of the feedstock, followed by distilling or fractionating the hydrocarbon process stream into different hydrocarbon groups. By cracking, reforming, and other conversion processes, the size and structure of hydrocarbon molecules are changed, and most of the distillation products are further converted into desired, more useful products or product intermediates. To remove unnecessary components or improve product quality, these converted products and / or intermediates can then be subjected to various treatment and separation processes, such as extraction, hydrotreating, and desulfurization. Integrated refining not only provides multiple separation and / or treatment steps such as fractionation, refining, treatment, and blending operations, but such refining can also include petrochemical processing.

[0003] The refining industry is highly dependent on certain important materials, including carbon steel and alloy steel, copper, aluminum, and non-ferrous alloys, for constructing petroleum refining equipment, such as pressure vessels, storage vessels, separation units, reactors, pumps, sensors, valves, columns, boilers, heat exchangers, condensers, pipelines, etc. However, the corrosion of these metal components is a major cause of inefficiency in the refining process, because corrosion leads to the deterioration of equipment, shortened service life, or even failure, and the refining industry spends a large amount of cost every year on maintenance, repair, replacement, etc. The corrosion risk usually intensifies with the increase in the operating temperature in the refining equipment.

[0004] Crude oil is a complex mixture of many different hydrocarbons and usually a relatively small fraction of non-hydrocarbons. In addition to hydrocarbons, crude oil can include not only other organic materials, but also sulfur, chlorine, nitrogen, and oxygen-containing compounds, such as gases, liquids, and solid phases dissolved in the oil. Many of these non-hydrocarbon components can be in the form of corrosives or corrosion precursor, which will erode the refining equipment.

[0005] Crude oil can be classified by two methods. The first is based on the proportion of organic compounds such as alkane compounds, cycloalkane compounds, aromatic compounds, or mixtures thereof. The second method of classifying crude oil is according to their American Petroleum Institute (API) gravity, which is usually 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 usually rich in paraffin and tend to produce a higher proportion of gasoline and light petroleum products. Low-carbon, low-hydrogen, and low-API gravity oils are usually relatively rich in aromatics.

[0006] Crude oil can contain entrained water and / or brine. Corrosive agents can be present in the hydrocarbon and / or aqueous portions of the crude oil. Corrosive agents that may be present 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 a large amount of hydrogen sulfide (H2S) is called "sour" crude oil, and crude oil with less H2S is called "sweet" crude oil.

[0008] Naphthenic acids are organic acids that are commonly present in crude oil and hydrocarbon streams during the refining and processing of oils. Naphthenic acids are corrosive to carbon steel and stainless steel, especially at higher temperatures (e.g., at or above 260 °C). In the high-temperature regions of a distillation system, the presence of naphthenic acids and / or sulfur compounds greatly increases corrosion. 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] To inhibit costly corrosion problems in the refining of oils, corrosion inhibitors are widely used in the petroleum recovery and processing industries. Corrosion inhibitors and / or other types of additives can be incorporated into corresponding formulations (also referred to as "compositions"), which are diluted to a certain extent with a solvent or used in an undiluted pure state. These formulations, with or without a solvent, can also include one or more other optional ingredients. Thus, the term "additive formulation" refers to a composition containing one or more additives, an optional solvent, and an optional one or more other ingredients. Similarly, as used herein, a "corrosion inhibitor" is an additive that helps prevent corrosion. As used herein, a "corrosion inhibitor formulation" is a composition containing one or more corrosion inhibitors, an optional solvent, and an optional one or more other ingredients. Such additive and corrosion inhibitor formulations can be provided in various forms, such as solids (e.g., powders, pellets, granules, blocks, etc.), liquids, dispersions, gels, putties, gases, etc. The liquid, solution, dispersion, and gel embodiments of these formulations tend to be more prone to stability problems associated with phase separation.

[0010] Prior to use or further processing, batches of the manufactured additive formulation are typically stored for a period of time. It is desirable that the additive formulation be stable during storage and / or transportation, e.g., for excessive phase separation into separate liquids, for precipitation of solids and / or gels, for sedimentation, or for other undesirable phase separations. Additive formulations that exhibit such changes may require special treatment to restore the additive formulation to its original state. It may even be impossible to return the additive formulation to its original state in a practical manner, and in its altered form, the additive formulation may be unusable. For example, in an additive formulation containing a precipitate, the settled material may not be pumpable or pourable. In any 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 refining may be acceptable, or even desirable, provided that the additive still provides the desired function (e.g., corrosion protection in the case of a corrosion inhibitor). In other cases, prevention of phase separation is desirable even during use in refining.

[0011] For addition to an industrial process stream or batch, such as a hydrocarbon processing stream or batch in an oil refining operation, the additive formulation can be conveniently 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. Since such solutions or dispersions of the additive are typically shipped and stored, it is economical if the solution or dispersion is relatively concentrated with respect to the additive, thereby avoiding the additional costs required to ship and store commodities such as organic solvents. Such solutions or dispersions provide flexibility because they can be easily further diluted at a more suitable time (such as at or near the point of use) if desired, and can be used without further dilution if a higher concentration is needed.

[0012] Like the additive itself, such solutions and / or dispersions of the additive or more dilute formulations are desirably sufficiently stable during storage, shipping, and use. Solutions, dispersions, and / or more dilute formulations of the additive are typically stored and / or transported in unheated winter environments where they reach temperatures, for example, of 0 °C or lower, -10 °C or lower, -20 °C or lower, -30 °C or even -40 °C or lower. Thus, it would be advantageous if corrosion inhibitor formulations and other additive formulations could be found to not excessively phase separate and / or sediment during storage, handling, or use, and not unduly separate even when provided in the form of a solution and / or dispersion in an organic solvent and stored, handled, transported, or otherwise used at low temperatures. SUMMARY OF THE INVENTION

[0013] We have found that additive compositions having a restricted glycerol content are more stable to phase separation. For example, if the vegetable oil fatty acid content has a reduced glycerol content, an additive composition incorporating one or more additives derived from vegetable oil fatty acids such as soybean oil fatty acids is more stable to phase separation. In a preferred embodiment, the additive composition having improved stability incorporates one or more additives derived from glycerol-restricted soybean oil fatty acids. In other embodiments, the formulation or one or more of its components can be processed to remove at least a portion of the glycerol content, thereby improving stability against phase separation.

[0014] We have also found that compositions of additives in organic solvents are more stable to precipitation (i.e., exhibit less or no precipitation) when made from glycerol-restricted vegetable oil fatty acids than equivalent concentrates made from tall oil fatty acids when stored for three weeks at temperatures such as 0 °C and -10 °C.

[0015] In one aspect, there is provided an additive composition comprising a plurality of amides and / or their ammonium salts, 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-restricted vegetable oil fatty acids and a polyamine, wherein the one or more glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more glycerol-restricted vegetable oil fatty acids, and wherein the polyamine comprises a polyamine having the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100. For example, if the one or more glycerol-restricted vegetable oil fatty acids consist of 0.06 parts by weight of glycerol and 100 parts by weight of soybean oil fatty acids, the total weight of the glycerol-restricted vegetable oil fatty acids is 100.06 parts by weight, and the glycerol content is 0.06 / 100.06 × 100% = 0.06%. The plurality of amides and / or their ammonium salts are used in some embodiments as corrosion inhibitor additives in additive compositions to help prevent corrosion.

[0016] In another aspect, a combined additive composition is provided that comprises a plurality of amides and / or their ammonium salts and further comprises a plurality of esters. At least a portion of the plurality of amides comprises a first reaction product derived from a first set of reactants that includes one or more glycerin-restricted vegetable oil fatty acids and a polyamine, wherein the one or more glycerin-restricted vegetable oil fatty acids comprise 0 wt% to 0.1 wt% glycerin relative to the total weight of the one or more glycerin-restricted vegetable oil fatty acids, and wherein the polyamine includes, consists of, or consists essentially of a polyamine having the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100. At least a portion of the plurality of esters comprises a second reaction product derived from a second set of reactants that includes one or more second glycerin-restricted vegetable oil fatty acids and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxy group, wherein the one or more second glycerin-restricted vegetable oil fatty acids comprise 0 wt% to 0.1 wt% glycerin relative to the total weight of the one or more second glycerin-restricted vegetable oil fatty acids. Individually, each of the plurality of amides and the plurality of esters, as well as a composition containing the plurality of amides or a composition containing the plurality of esters, can be used in a variety of applications, such as for corrosion inhibition. However, the combination of the plurality of amides and the plurality of esters and a composition containing these combinations is particularly effective in corrosion inhibition.

[0017] In another aspect, a composition comprising heavy aromatic naphtha and an additive is provided, the additive comprising a plurality of amides and / or their ammonium salts, wherein at least a portion of the plurality of amides comprises a reaction product derived from a first set of reactants that includes one or more glycerin-restricted vegetable oil fatty acids and a polyamine, wherein the one or more glycerin-restricted vegetable oil fatty acids comprise 0 wt% to 0.1 wt% glycerin relative to the total weight of the one or more glycerin-restricted vegetable oil fatty acids, and wherein the polyamine has the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100. The reaction product derived from the first set of reactants can be conveniently 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 heavy aromatic naphtha is added to one or more hydrocarbons in a convenient form to impart desired properties thereto, such as corrosion inhibition, anti-fouling properties, and / or other desired properties. Heavy aromatic naphtha is generally miscible with hydrocarbons, and thus, when added to one or more hydrocarbons, the composition can be dispersed in the one or more hydrocarbons, thereby imparting improved characteristics thereto.

[0018] In another aspect, there is provided a composition comprising heavy aromatic naphtha, its various amides and / or ammonium salts, and further comprising various esters. At least a portion of the various amides comprises a first reaction product derived from a first set of reactants comprising one or more first glycerol-restricted vegetable oil fatty acids and a polyamine, wherein the one or more first glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more first glycerol-restricted vegetable oil fatty acids, and wherein the polyamine comprises a polyamine having the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100. At least a portion of the various esters comprises a second reaction product derived from a second set of reactants comprising one or more second glycerol-restricted vegetable oil fatty acids and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxyl group, wherein the one or more second glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more second glycerol-restricted vegetable oil fatty acids. Individually, each of the various amides, their ammonium salts, and the various esters, and compositions containing them, can be used in a variety of applications, such as for inhibiting corrosion. However, the combination of the various amides and the various esters, and compositions containing these combinations, are particularly effective in inhibiting corrosion.

[0019] In another aspect, there is provided a composition comprising more than 5 wt% water relative to the total weight of the composition and an additive comprising an ammonium salt of various amides, wherein at least a portion of the various amides comprises a reaction product derived from a set of reactants comprising one or more glycerol-restricted vegetable oil fatty acids and a polyamine, wherein the one or more glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more glycerol-restricted vegetable oil fatty acids, and wherein the polyamine has the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100. The ammonium salt can be more water-soluble and / or water-dispersible than the amide, and thus the composition can be particularly useful for adding to aqueous materials to impart desired properties, such as imparting corrosion inhibition properties or dispersant properties in an aqueous system.

[0020] In another aspect, there is provided a hydrocarbon composition 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 amide compositions, ester compositions, and combinations thereof. The amide composition comprises a plurality of amides, 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 first glycerol-restricted vegetable oil fatty acids and a polyamine, wherein the one or more first glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more first glycerol-restricted vegetable oil fatty acids, and wherein the polyamine has the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100; and wherein the ester composition comprises a plurality of esters, wherein at least a portion of the plurality of esters comprises a second reaction product derived from a second set of reactants comprising one or more second glycerol-restricted vegetable oil fatty acids and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxy group, wherein the one or more second glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more second glycerol-restricted vegetable oil fatty acids. Incorporating the additive composition into the one or more hydrocarbons can impart corrosion-inhibiting properties to the combination of the one or more hydrocarbons and the additive composition, or can inhibit or otherwise improve the corrosion of metal components in contact with the one or more hydrocarbons by corrosion agents therein.

[0021] In another aspect, there is provided a method of providing corrosion protection to a surface in contact with one or more hydrocarbons, the method comprising combining a corrosion inhibitor composition with the one or more hydrocarbons, wherein the corrosion inhibitor composition comprises a plurality of amides and / or their ammonium salts, 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-restricted vegetable oil fatty acids and a polyamine, wherein the one or more glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more glycerol-restricted vegetable oil fatty acids, and wherein the polyamine has the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100. These methods can be used, for example, in petroleum or other hydrocarbon industrial processing facilities, wherein adding the corrosion inhibitor composition to the one or more hydrocarbons can inhibit the corrosion of metal components in contact with the one or more hydrocarbons.

[0022] In another aspect, a method for preparing an additive composition is provided, the additive composition comprising a first reaction product. The method includes: combining one or more glycerol-restricted vegetable oil fatty acids with a polyamine to form a first reaction mixture, wherein the one or more glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more glycerol-restricted vegetable oil fatty acids; optionally adding a hydrocarbon solvent to the first reaction mixture; heating the first reaction mixture at a reaction temperature 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 can be used to be added to, for example, hydrocarbon process streams and batches in industrial processes to impart corrosion inhibition properties thereto.

[0023] In another aspect, a method for preparing a combined additive composition is provided, the method including: combining one or more first glycerol-restricted vegetable oil fatty acids with a polyamine to form a first reaction mixture, wherein the one or more first glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol relative to the total weight of the one or more first glycerol-restricted vegetable oil fatty acids; optionally adding a hydrocarbon solvent to the first reaction mixture; heating the first reaction mixture at a reaction temperature for a period of time effective to form water and a first reaction product, the first reaction product comprising a plurality of amides; combining one or more second glycerol-restricted vegetable oil fatty acids with one or more tertiary amines, each of the one or more tertiary amines comprising at least one hydroxyl group, to form a second reaction mixture; heating the second reaction mixture at a reaction temperature for a period of time effective to form a second product mixture comprising water and a second reaction product, wherein the second reaction product comprises a plurality of esters; combining the components comprising the first reaction product and the second reaction product to form the combined additive composition. The combination of the first reaction product and the second reaction product and the composition comprising the combination can be used as, for example, a corrosion inhibitor to be added to a hydrocarbon stream to impart corrosion inhibition properties thereto. Detailed Description

[0024] Although the present disclosure provides references 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 will be described in detail with reference to the accompanying drawings. The reference to various embodiments does not limit the scope of the appended claims herein. Additionally, any examples set forth in this application are illustrative and not intended to be limiting, and merely set forth some of the many possible embodiments for 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) shall prevail. Methods and materials are described below, but methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety and for all purposes.

[0027] As used herein, the terms "comprising", "including", "having", "may", "containing", and their variants are intended to be open transitional phrases, terms, or words that do not exclude the possibility of additional acts or structures. Unless the context clearly dictates otherwise, the singular forms "a", "and", and "the" include plural referents.

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

[0029] As used herein, any range of values encompasses all values within the stated range and should be interpreted as supporting claims reciting any sub-range having endpoints within the stated range. For example, the disclosure of a range of 1 to 5 in this specification should be considered to support claims for any of the following ranges: 1 - 5; 1 - 4; 1 - 3; 1 - 2; 2 - 5; 2 - 4; 2 - 3; 3 - 5; 3 - 4; and 4 - 5; and their decimals, such as 1.5 - 3.5, 1.7 - 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 "vegetable oil fatty acids". Since a single type of vegetable oil contains esters of multiple 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" along with the by-product glycerol. Although used in the singular form, 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 may vary in composition (e.g., in terms of the relative content of various fatty acid compounds in ester form). However, the type and range of each fatty acid compound in vegetable oil fatty acids are typically characteristic of the type of vegetable oil from which the vegetable oil fatty acids may be derived. Although the term "vegetable oil fatty acids" used in the singular form refers to a combination of fatty acid compounds that can be produced by hydrolysis of the vegetable oil of the same name, "vegetable oil fatty acids" 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-restricted" with respect to a material generally means that the material contains no more than 0.1% by weight of glycerol, based on the weight of the material (including glycerol, if any). For example, a "glycerol-restricted fatty acid amide" refers to a material containing a fatty acid amide, wherein the material contains no more than 0.1% by weight of glycerol, based on the weight of the glycerol-restricted fatty acid amide.

[0032] The term "glycerol-restricted vegetable oil fatty acid" refers to a mixture containing no more than 0.1% by weight of glycerol and no less than 99% by weight of fatty acids, relative to the mixture. Glycerol-restricted vegetable oil fatty acids can be prepared in various ways. One commercially important way to prepare glycerol-restricted vegetable oil fatty acids is to hydrolyze the vegetable oil of the same name and then purify it to remove glycerol, which is a by-product of hydrolysis. The type of fatty acid and its proportion in the glycerol-restricted vegetable oil fatty acid depend on the composition of the hydrolyzed vegetable oil, especially the type of vegetable oil, i.e., the type of plant from which the vegetable oil is derived. For example, while soybean oil as a natural product may vary in terms of the composition of its fatty acid esters, it can vary within the range characteristic of soybean oil. However, in principle, glycerol-restricted vegetable oil fatty acids can also be produced by mixing the correct types of fatty acids in the correct proportions, and for which the cumulative glycerol content (if any) is low enough such that the resulting mixture is glycerol-restricted, as defined according to the present invention. In such an embodiment, a certain degree of purification to reduce the glycerol content is not required, since the fatty acid material is appropriately glycerol-restricted at the start. For illustrative purposes only, a glycerol-restricted soybean oil fatty acid may contain, in a specific example, 10% by weight of palmitic acid, 4% by weight of stearic acid, 23% by weight of oleic acid, 51% by weight of linoleic acid, and 9% by weight of α-linolenic acid, based on the total weight of the fatty acids. Such a glycerol-restricted soybean oil fatty acid can in principle be produced by mixing 10 parts by weight of palmitic acid, 4 parts by weight of stearic acid, 23 parts by weight of oleic acid, 51 parts by weight of linoleic acid, 9 parts by weight of α-linolenic acid, and any other components of the glycerol-restricted soybean oil fatty acid, wherein the glycerol is restricted at the time of supply, or the mixture is purified to remove glycerol.

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

[0034] As used herein, "polyamine", "a polyamine", and "the polyamine" are interpreted to mean discrete compounds having a single molecular weight, such as tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2), and combinations of individual polyamine compounds. For example, a polyamine can have the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100. In this particular example, if the polyamine is a discrete polyamine compound, the value of x is an integer, but if the polyamine is a mixture of discrete polyamine compounds having different molecular weights, x can also be a fraction or a mixed fraction. As used herein, the term "polyamine" is used not only to refer to discrete polyamine compounds, although it can, but also to mixtures and / or combinations of discrete polyamine compounds. A polyamine can include 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 amines.

[0035] As used herein, the term "concentrate" generally refers to a composition in which the concentration of an additive is higher than the concentration of such additive after the composition is diluted for its intended use. A concentrate can be a solid, liquid, dispersion, gel, or gas. A concentrate can contain or not contain a solvent until further dilution. In a representative embodiment, prior to dilution with a solvent, per 100 parts by weight of the additive, the concentrate can contain from 0 parts to 80 parts, or even from 0 parts to 50 parts, or even from 0 parts to 25 parts, or even from 0 parts to 10 parts of a solvent. If desired, the concentrate can be diluted by adding an amount of additional solvent, which can be the same as and / or different from the solvent in the concentrate. By way of example, dilution can be carried out by adding from 1 part to 1000 parts by weight, or even from 10 parts to 500 parts by weight, or even from 10 parts to 100 parts by weight of additional solvent per 50 parts to 100 parts by weight of the solvent in the concentrate.

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

[0037] Discussion

[0038] Fatty acid amides have been put into commercial practice as corrosion inhibitors or as other types of additives, for example, in the refining of oils. In conventional practice, fatty acid amides are prepared by reacting tall oil or tall oil fatty acids with amines. Tall oil and tall oil fatty acids (TOFA) are already a convenient source of fatty acids. Tall oil is a by-product of the sulfate process for wood pulp manufacture. Generally, crude tall oil contains: rosin, which contains resin acids (mainly abietic acid and its isomers); a mixture of fatty acids (mainly palmitic acid, oleic acid, and linoleic acid); fatty alcohols; sterols; and other alkyl hydrocarbon derivatives. Tall oil fatty acids are a purified form of tall oil and contain a lower weight percentage of rosin (1 wt% to 10 wt%) than tall oil. Tall oil fatty acids include fatty acids, mainly oleic acid.

[0039] Tall oil fatty acids (TOFA) can be reacted with one or more amines to produce TOFA amides, which are reaction products of a mixture containing fatty acid amides and other components derived from the resin acids in TOFA. The reaction can be summarized as follows:

[0040] Solution 1

[0041] TOFA + amine → mixture of fatty acid amides + other components + water

[0042] TOFA-derived fatty acid amides can be used as corrosion inhibition additives, for example, in the refining of crude oil or other processed hydrocarbon streams. Conveniently, additive compositions incorporating such additives into hydrocarbon streams can be provided as concentrates in organic solvents. The concentrate (as is or in diluted form) is stored, transported, and provided to an oil processing plant for addition to the hydrocarbon stream therein. However, when stored for a period of days or weeks at lower temperatures (such as 0 °C or lower, -10 °C or lower, or -20 °C or lower), the concentrate or even the diluted form of such additives may be unstable, exhibiting precipitation, other phase separation, or other instabilities, such that the affected composition cannot be easily redissolved or redispersed. For example, a corrosion inhibition composition incorporating the reaction product of TOFA and 2-aminoethyl ethanolamine (AEEA) exhibits precipitation after only a few days at each of 0 °C, -10 °C, or -20 °C. Long-term storage, such as storage at -10 °C or -20 °C for 64 days, produces precipitates that cannot be redissolved even after warming to room temperature (15 °C to 25 °C or about 20 °C). Thus, the concentrate or even the diluted form of corrosion inhibitors from TOFA sources as conventionally used may be more unstable at colder temperatures than desired. Without being bound by theory, we speculate that this instability may be a direct or indirect result of the rosin content in TOFA.

[0043] Although the abietic acid content can be removed using separation techniques, another drawback is more difficult to overcome. It has become increasingly difficult to obtain tall oil or TOFA materials from commercial sources at an economical price. Therefore, there is an increasing desire to find fatty amide materials that can be more easily obtained as substitutes for tall oil or TOFA materials.

[0044] Fatty amides can also be prepared by the reaction of vegetable oils with one or more amines. Vegetable oils include glycerides, mainly triglycerides. Glycerides are esters of glycerol (propane-1,2,3-triol) and fatty acids. Fatty amides derived from vegetable oils show great potential as alternative corrosion inhibitors to 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 contain a trace amount of abietic acid content (if any) as natural substances. Unfortunately, the technical challenges associated with using such materials involve stability. We have found that additives made from vegetable oils and incorporated with glycerol tend to have poor stability in terms of undergoing phase separation.

[0045] Notably, the practice of the present invention provides a technical solution for providing more stable fatty amides from vegetable oil sources. Thus, the fatty amide materials of the present invention can be used as substitutes for all or part of the previously used tall oil and TOFA materials.

[0046] Since vegetable oils contain a mixture of glycerides, when reacted with even a single type of amine, a mixture of fatty amides is obtained. The general reaction between vegetable oil and amine can be summarized as follows, where glycerol is a by-product:

[0047] Solution 2

[0048] Vegetable oil + Amine → Mixture of fatty amides + Glycerol

[0049] Alternatively, one or more vegetable oils can be hydrolyzed to produce hydrolyzed vegetable oil, which contains a mixture of fatty acids and the by-product glycerol. The hydrolyzed vegetable oil (fatty acids and glycerol) can then be reacted with an amine to produce fatty amides along with glycerol. The reaction can be summarized as follows:

[0050] Solution 3

[0051] (i) Vegetable oil + Water → Hydrolyzed vegetable oil (Mixture of fatty acids + Glycerol)

[0052] (ii) Hydrolyzed vegetable oil + Amine → Mixture of fatty amides + Glycerol + Water

[0053] In Processes 2 and 3, other components may be present. For example, the hydrolysis of the vegetable oil represented by Reaction (i) of Process 3 may be catalyzed by an acid or a base. It should also be understood that, depending on the pH, the fatty acids may be present in the form of their salts.

[0054] As can be seen from Processes 2 and 3, the production of fatty amide additives from vegetable oils provides reaction products that include glycerol. The reaction products of the vegetable oil and the amine may be prone to phase separation. Without wishing to be bound by theory, we believe that the presence of the by-product glycerol in the intermediate and then in the fatty amide product provides an additive composition that is more prone to phase separation and thus less stable compared to a similar additive composition that is at least partially purified with respect to glycerol. In other words, when using fatty amide additives derived from vegetable oils in an additive composition, the stability is improved by using an additive composition with a reduced glycerol content.

[0055] According to the present invention, reduced glycerol fatty amide additives can be prepared according to a reaction such as that shown in Scheme 4a:

[0056] Solution 4a

[0057] (i) Vegetable oil + water → Hydrolyzed vegetable oil (fatty acids + glycerol)

[0058] (ii) Hydrolyzed vegetable oil - glycerol → Glycerol-restricted vegetable oil fatty acids (VOFA)

[0059] (iii) Glycerol-restricted vegetable oil fatty acids + polyamine → Glycerol-restricted vegetable oil fatty acid amide + water

[0060] For example, as shown in Scheme 4b, the reaction product of tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2) (TEPA) with glycerol-restricted fatty amides of soybean oil fatty acids is much more stable and more resistant to phase separation than the fatty amides prepared by Processes 2 and 3.

[0061] Solution 4b

[0062] (i) Soybean oil + water → Hydrolyzed soybean oil (fatty acids + glycerol)

[0063] (ii) Hydrolyzed soybean oil - glycerol → Glycerol-restricted soybean oil fatty acids (SOFA)

[0064] (iii) Glycerol-restricted soybean oil fatty acids + tetraethylenepentamine → Glycerol-restricted soybean oil fatty acid amide + water

[0065] Glycerol-restricted soybean oil fatty acids (SOFA) are commercially available.

[0066] Glycerol-restricted vegetable oil fatty acids, including fatty acids derived from soybean oil, can be produced according to Scheme 4a(i) to Scheme 4a(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 (such as in the range of 30 °C to 100 °C, for example 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 (such as 1 hour to 24 hours, for example 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) to effectively saponify one or more vegetable oils to a desired degree of completion. Saponification and hydrolysis of one or more vegetable oils produce fatty acid salts and by-product glycerol. To produce free fatty acids from the fatty acid salts, the pH of the mixture is lowered by adding an inorganic acid such as sulfuric acid, hydrochloric acid or a combination thereof. For example, the pH can be lowered to 1 to 4, or 1 to 3, or about 2. The aqueous phase containing water, salts of inorganic acids and glycerol is separated from the organic phase into different layers, and the aqueous phase is separated from the organic phase. The organic phase can be dried. The organic phase can be further purified by separating into fractions, each fraction having a different range of acid values. For the present invention, the glycerol-restricted vegetable oil fatty acids can be derived from fractions having an acid value of 170 mg KOH / g to 230 mg KOH / g, or 180 mg KOH / g to 220 mg KOH / g, or 190 mg KOH / g to 210 mg KOH / g, or about 192 mg KOH / g to 205 mg KOH / g. For example, the glycerol-restricted vegetable oil fatty acids can comprise, consist of or consist essentially of glycerol-restricted soybean oil fatty acids having an acid value of about 192 mg KOH / g to about 205 mg KOH / g.

[0067] Without wishing to be bound by theory, we believe that hydrolyzing the glycerol in soybean oil and / or its reaction products renders the resulting additive composition unstable. Thus, removing at least part of the glycerol content from the components or their precursors provides an additive composition with improved stability.

[0068] As other embodiments of the present invention, combination additive compositions are disclosed herein that comprise a mixture of the glycerol-restricted fatty amide additives of Scheme 4a or Scheme 4b combined with a variety of fatty esters. To improve stability, it is preferred that the fatty esters are also glycerol-restricted to the same reduced concentration range as the glycerol-restricted fatty amides of Scheme 4a and Scheme 4b. The combination additive compositions of the present invention can be used in the processing and refining industries of oils for applications similar to amides, for example, to prevent corrosion.

[0069] For example, fatty esters can be prepared by transesterification, as shown in Scheme 5.

[0070] Solution 5

[0071] Vegetable oil + alcohol → glycerol + multiple esters

[0072] Scheme 5 shows that fatty esters can generally be prepared by reacting one or more vegetable oils with one or more alcohols in a transesterification reaction. A preferred vegetable oil is soybean oil.

[0073] The alcohols suitable for Scheme 5 can be primary alcohols, secondary alcohols, tertiary alcohols, 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 comprises three ethanol moieties (each comprising a primary OH group) coupled to a central N atom.

[0074] However, the reaction product of Scheme 5 again contains glycerol. The practice of the present invention teaches removing all or part of the glycerol to improve the stability of the additive composition incorporated into the fatty ester product. Thus, in the practice of the present invention, the product mixture of Scheme 5 can be at least partially purified with respect to glycerol to provide the glycerol-restricted fatty esters of the present invention.

[0075] Alternatively, a preferred method for preparing multiple fatty esters is by the reaction of an alcohol with one or more glycerol-restricted vegetable oil fatty acids, such as a hydrolyzed vegetable oil that has been purified with respect to glycerol, as exemplified in Scheme 6, where the exemplified vegetable oil is soybean oil and the exemplified alcohol is triethanolamine:

[0076] Solution 6

[0077] (i) Soybean oil + water → hydrolyzed soybean oil (soybean oil fatty acids + glycerol)

[0078] (ii) Hydrolyzed soybean oil - glycerol → glycerol-restricted soybean oil fatty acids (SOFA)

[0079] (iii) Glycerol-restricted soybean oil fatty acids + triethanolamine → SOFA-TEA ester additive + water

[0080] When implementing Scheme 6(iii), the general reaction for forming a fatty ester from a fatty acid (represented by RCOOH) and triethanolamine (which is a triol) can be represented as follows in Scheme 7 (where each R independently represents a straight-chain, branched-chain, or cyclic hydrocarbon group):

[0081] Scheme 7

[0082]

[0083] 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. In addition, since glycerol-restricted vegetable oil fatty acids such as glycerol-restricted soybean oil fatty acids contain a mixture of fatty acids, the reaction of glycerol-restricted vegetable oil fatty acids with TEA is expected to produce a more complex mixture of monoester, diester, and triester reaction products. The use of diols, tetraols, or other alcohols with multiple OH groups also results in a product mixture. When the alcohol has at least one chiral carbon, the product mixture may be even more complex because even more monoester, diester, triester, etc. products may be produced.

[0084] The esterification reaction between glycerol-restricted soybean oil fatty acids (SOFA, which contains a mixture of fatty acids) and triethanolamine (TEA) can be represented as follows:

[0085] Solution 8

[0086] SOFA + triethanolamine - H2O → SOFA-TEA esters (mixture of esters)

[0087] The method for preparing an additive disclosed herein can provide fatty amide and / or fatty ester reaction products that contain little or no glycerol, no abietic acid and / or its derivatives, and little or no reaction products of glycerol and resin acids, for example, fatty amide and / or fatty ester reaction products that are no more than 0.1 weight percent (wt%) relative to the weight of the corresponding additive. The method uses glycerol-restricted vegetable oil fatty acids, which react with amines to produce fatty amides with restricted glycerol content. The use of glycerol-restricted vegetable oil fatty acids in the method herein can produce additives with restricted glycerol content (e.g., 0.1 wt% or less of glycerol relative to the total weight of the fatty acid content).

[0088] Contrary to tall oil or tall oil fatty acids, the use of glycerol-restricted vegetable oil fatty acids avoids abietic acid content, such as abietic acid or its derivatives. Abietic acid content is a natural component of tall oil and tall oil fatty acids. Due to its acidic nature, abietic acid may tend to be a corrosive agent in refining equipment. Therefore, avoiding abietic acid is highly desirable. Advantageously, soybean oil and many other vegetable oils have little (if any) abietic acid content. Thus, fatty amides and fatty esters derived from soybean oil and other vegetable oils avoid the corrosion risk associated with abietic acid. Unfortunately, however, additives derived from vegetable oils are prone to phase separation, thus reducing the attractiveness of using such additives. However, the present invention teaches how to improve the stability of these materials, making their use practical and desirable. Significantly, the present invention not only avoids abietic acid corrosive agents but also allows more stable vegetable oil source materials to be used for corrosion protection.

[0089] The first embodiment of the present invention

[0090] These embodiments illustrate glycerol-restricted fatty acid amides, which can be derived from one or more vegetable oils and subsequently used as additives in additive compositions for various purposes, such as to prevent corrosion in oil refining facilities or other environments where corrosion protection is desired. Thus, in a first embodiment of the present invention, a first additive composition is provided. The first additive composition comprises a first reaction product, consists of or consists essentially of the first reaction product. The first additive composition may comprise the first reaction product and one or more solvents, consist of or consist essentially of them. The first additive composition may comprise the first reaction product and one or more optional ingredients, consist of or consist essentially of them. The first additive composition may comprise the first reaction product, one or more solvents and other optional ingredients, consist of or consist essentially of them. The other optional ingredients may be selected from a wide range of materials, including but not limited to one or more of anti-polymerization agents, antioxidants, amines, foaming agents, dispersants, and phenol-formaldehyde polymers.

[0091] The first reaction product comprises a plurality of amides, consists of or consists essentially of them.

[0092] The plurality of amides can be synthesized by reacting a first set of reactants to produce the first reaction product and water, as shown in Scheme 9, where the glycerol-restricted vegetable oil fatty acid is represented by VOFA, and where -H2O represents the removal of water during and / or after the reaction:

[0093] Solution 9

[0094] VOFA + polyamine (+ optional one or more solvents) -H2O ———→

[0095] First reaction product (+ optional one or more solvents)

[0096] As described in Scenario 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, the first additive composition comprises, consists of, or consists essentially of the first reaction product and one or more solvents. Whether the reaction is carried out in a solvent or not, a solvent or additional solvents can subsequently be added to the reaction product to form a concentrate, as described in the third embodiment 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 olefins. Examples of suitable hydrocarbons include, but are not limited to, benzene, toluene, xylene (ortho-xylene, meta-xylene, para-xylene, and any combination thereof), heavy aromatic naphtha (HAN), C5 to C17 alkanes, olefins, and naphtha, one or more of them.

[0097] The first group of reactants comprises, consists of, or consists essentially of one or more glycerol-restricted vegetable oil fatty acids and polyamines.

[0098] The first reaction product can comprise, consist of, or consist essentially of a plurality of amides, or the first reaction product can comprise a plurality of amides and one or more by-products, consisting of or consisting essentially of them. 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-restricted vegetable oil fatty acids in the present invention advantageously provides a first reaction product that is free of glycerol or contains less than 0.1% by weight of glycerol relative to the weight of the first reaction product, without further purifying the first reaction product.

[0099] As described in Scenario 4a(iii), the reaction of a polyamine with glycerol-restricted vegetable oil fatty acids can produce glycerol-restricted vegetable oil fatty acid amides and a by-product water. The glycerol-restricted vegetable oil fatty acid amides comprise, consist of, or consist essentially of a plurality of amides. The first reaction product can consist of or consist essentially of amides, or the first reaction product can comprise amides and by-products and / or other substances, consist of them, or consist essentially of them. The first reaction product can comprise from about 99 wt% to 100 wt% amides, or from about 95 wt% to 100 wt% amides, or from about 98 wt% to 100 wt% amides, or from about 97 wt% to 100 wt% amides, or from about 96 wt% to 100 wt% amides, or from about 95 wt% to 99.5 wt% amides, or from about 96 wt% to 99.5 wt% amides, or from about 97 wt% to 99.5 wt% amides, or from about 98 wt% to 99.5 wt% amides, or from about 99 wt% to 99.5 wt% amides, or from about 90 wt% to 100 wt% amides, or from about 80 wt% to about 100 wt% amides, or from about 90 wt% to about 99.5 wt% amides, or from about 80 wt% to about 99.5 wt% amides, based on the weight of the first reaction product.

[0100] Preferably, water (by-product) is separated from the glycerol-restricted vegetable oil fatty acid amides. Conveniently, at least a portion or even most or all of the by-product water can be removed during the reaction. Removing water during the reaction helps to drive the amide formation reaction forward. Thus, the dried first reaction product can comprise, consist of, or consist essentially of a plurality of amides and any by-products (if any). In this context, "consist essentially of" allows for a small amount of water to be present in the amides: even when dried or partially dried, the amides can contain a small amount of residual water from the reaction and / or some water taken from the environment. The first reaction product can comprise from about 0 wt% to 1 wt% water, or from about 0 wt% to 5 wt% water, or from about 0 wt% to 2 wt% water, or from about 0 wt% to 3 wt% water, or from about 0 wt% to 4 wt% water, or from about 0.5 wt% to 5 wt% water, or from about 0.5 wt% to 4 wt% water, or from about 0.5 wt% to 3 wt% water, or from about 0.5 wt% to 2 wt% water, or from about 0.5 wt% to 1 wt% water, or from about 0 wt% to 10 wt% water, or from about 0 wt% to about 20 wt% water, or from about 0.5 wt% to about 10 wt% water, or from about 0.5 wt% to about 20 wt% water, based on the weight of the plurality of amides.

[0101] Preferably, the first reaction product mainly or only contains amide, and does not contain or contains a minimal amount of glycerol, does not contain or contains a minimal amount of rosin acid, does not contain or contains a minimal amount of imidazoline content, and does not contain or contains a minimal amount of water. The first reaction product may contain, by weight relative to the total fatty amide content in the first reaction product, 0 wt% to 1 wt%, or 0 wt% to 2 wt%, or 0 wt% to 3 wt%, or 0 wt% to 4 wt%, or 0 wt% to 5 wt%, or 0 wt% to 0.1 wt%, or 0 wt% to 0.01 wt%, or 0 wt% of each of the following types of materials in total: rosin acid, salts of rosin acid, amides of rosin acid, esters of rosin acid, fatty acid esters, imidazoline, and C1-C10 monohydric alcohols.

[0102] The first reaction product can be used without further purification to provide a first additive, which can be further purified before use, or other materials such as additional fatty acid amides can be added to the first reaction product to provide a first additive, provided that the other materials do not contain rosin acid and its derivatives and contain less than 0.1 wt% of glycerol by weight relative to the other materials.

[0103] The first group of reactants may contain, consist of, or consist essentially of one or more glycerol-restricted 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 straight-chain, branched-chain, or cyclic, and can be aliphatic or aromatic. Preferred polyamines have a linear carbon backbone and are aliphatic.

[0104] In a preferred embodiment, the polyamine contains a linear carbon backbone, contains at least one primary terminal amine moiety and preferably terminal primary amine moieties at each end, and contains one or more secondary amine moieties and / or tertiary amine moieties pendant from the carbon backbone. In a preferred embodiment, the polyamine may have the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 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 where x is 3. In any embodiment and implementation herein, the polyamine may contain, consist of, or consist essentially of tetraethylenepentamine (TEPA) (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2).

[0105] One or more glycerol-restricted vegetable oil fatty acids for preparing the amides in Scheme 9 can be selected from one or more of the following: glycerol-restricted avocado oil fatty acids, rapeseed oil fatty acids, coconut oil fatty acids, corn oil fatty acids, cottonseed oil fatty acids, grapeseed oil fatty acids, hazelnut oil fatty acids, hempseed oil fatty acids, linseed oil fatty acids, olive oil fatty acids, palm oil fatty acids, palm kernel oil fatty acids, peanut oil fatty acids, rapeseed oil fatty acids, rice bran oil fatty acids, safflower oil fatty acids, sesame oil fatty acids, glycerol-restricted soybean oil fatty acids, sunflower oil fatty acids, and walnut oil fatty acids. In some preferred embodiments and aspects disclosed herein, one or more glycerol-restricted vegetable oil fatty acids can comprise, consist of, or consist essentially of glycerol-restricted soybean oil fatty acids.

[0106] One or more glycerol-restricted vegetable oil fatty acids can comprise from 0 wt% to 0.01 wt%, or from 0 wt% to 0.02 wt%, or from 0 wt% to 0.03 wt%, or from 0 wt% to 0.05 wt%, or from 0.05 wt% to 0.1 wt%, or about 0 wt% glycerol, based on the total weight of the one or more glycerol-restricted vegetable oil fatty acids.

[0107] One or more glycerol-restricted vegetable oil fatty acids can comprise, consist of, or consist essentially of glycerol-restricted soybean oil fatty acids. Glycerol-restricted soybean oil fatty acids can be hydrolyzed soybean oil that has been purified with respect to glycerol. Although the composition of soybean oil as a natural product can vary, the composition of soybean oil tends to fall within certain ranges. Glycerol-restricted soybean oil fatty acids can comprise, consist of, or consist essentially of the following: about 2 wt% to 15 wt% alpha-linolenic acid, about 46 wt% to about 56 wt% linoleic acid, about 17 wt% to about 28 wt% oleic acid, about 1 wt% to about 10 wt% stearic acid, and about 5 wt% to about 15 wt% palmitic acid and / or their corresponding salts, based on the weight of the glycerol-restricted soybean oil fatty acids. For clarity, the weight of the glycerol-restricted soybean oil fatty acids includes the glycerol content (if any).

[0108] In an exemplary embodiment, glycerin-restricted 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, stirrer, nitrogen inlet, and Dean-Stark apparatus. Heavy aromatic naphtha (HAN) (18.3 parts by weight) is added to the combination to form a mixture. Nitrogen purging 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 compensate for the amount of HAN lost to the Dean-Stark water separator. The contents of the flask are stirred for an additional 10 minutes and allowed to cool to room temperature to provide an additive composition. The additive composition comprises a plurality of amides and HAN. The additive can be used in a variety of applications, including as a corrosion inhibitor.

[0109] The first additive as described in the first embodiment of the present invention can be used as an efficient corrosion inhibitor, dispersant, lubricant, defoamer, foaming agent, and / or stripping agent in an additive composition. In a preferred embodiment, the first additive is used in a corrosion inhibition composition. More preferably, such compositions can be used to prevent corrosion in an oil refining facility. In such a facility, the composition can be added to one or more process streams, whereby the presence of the additive in the stream helps protect the equipment surfaces in contact with the treated process stream from corrosion. Additionally, or alternatively, the composition can be used to passivate the equipment surfaces before they come into contact with the treated and / or untreated process streams.

[0110] However, a combined additive comprising, consisting of, or consisting essentially of a combination of the first reaction product as described above and a second reaction product as described below may be more effective as a corrosion inhibitor, dispersant, lubricant, defoamer, foaming agent, and / or stripping agent. The second reaction product comprises one or more fatty acid esters, preferably glycerin-restricted fatty acid esters derived from one or more vegetable oil fatty acids, as listed herein with respect to Scheme 9.

[0111] The second embodiment of the present invention

[0112] This embodiment illustrates how the glycerol-restricted fatty acid amides described in Scheme 9 can be used in combination with glycerol-restricted fatty acid esters also derived from one or more vegetable oils. The combination can be used as an additive in an additive composition for various purposes, such as those listed in Scheme 9, preferably for anti-corrosion in an oil refining facility or in other environments where anti-corrosion is required. Thus, in a second embodiment of the present invention, there is provided a combined additive comprising, consisting of, or consisting essentially of the first reaction product and the second reaction product as described above. The weight ratio of the first reaction product to the second reaction product in the combined additive, or alternatively the weight ratio of the total fatty amide to the total fatty ester, 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. While the first reaction product comprises a plurality of fatty acid amides, the second reaction product comprises a plurality of fatty acid esters.

[0113] The second reaction product can be prepared as shown in Scheme 10, where VOFA is a glycerol-restricted vegetable oil fatty acid:

[0114] Solution 10

[0115] VOFA + tertiary amine (+ optional one or more solvents) - H2O ———→

[0116] Second reaction product (+ optional one or more solvents)

[0117] 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, the second set of reactants comprising, consisting of, or consisting essentially of a second set of one or more glycerol-restricted 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-restricted vegetable oil fatty acids can comprise, consist of, or consist essentially of one or more hydrolyzed vegetable oils purified with respect to glycerol.

[0118] As shown in Scheme 10, the reaction produces a second reaction product and a by-product water. Preferably, at least a part or even most or all of the water (i.e., the reaction by-product) is removed during the reaction.

[0119] Preferably, water (a by-product) is separated from the reaction mixture. Conveniently, at least a part or even most or all of the by-product water can be removed during the reaction. Removing water during the reaction helps to drive the ester formation reaction forward. Thus, the dried second reaction product can comprise, consist of, or consist essentially of various esters and any by-products (if any). In this context, "consist essentially of" allows for a small amount of water to be present in the ester: even when dried or partially dried, the ester can contain a small amount of residual water from the reaction and / or some water taken from the environment. The second reaction product can contain about 0 wt% to 1 wt%, or about 0 wt% to 5 wt%, or about 0 wt% to 2 wt%, or about 0 wt% to 3 wt%, or about 0 wt% to 4 wt%, or about 0.5 wt% to 5 wt%, or about 0.5 wt% to 4 wt%, or about 0.5 wt% to 3 wt%, or about 0.5 wt% to 2 wt%, or about 0.5 wt% to 1 wt%, or about 0 wt% to 10 wt%, or about 0 wt% to about 20 wt%, or about 0.5 wt% to about 10 wt%, or about 0.5 wt% to about 20 wt% water, based on the weight of the various esters.

[0120] The second reaction product can consist of or consist essentially of esters, or the second reaction product can comprise esters and by-products and / or other substances and consist of or consist essentially of them. The second reaction product can contain about 99 wt% to 100 wt%, or about 95 wt% to 100 wt%, or about 98 wt% to 100 wt%, or about 97 wt% to 100 wt%, or about 96 wt% to 100 wt%, or about 95 wt% to 99.5 wt%, or about 96 wt% to 99.5 wt%, or about 97 wt% to 99.5 wt%, or about 98 wt% to 99.5 wt%, or about 99 wt% to 99.5 wt%, or about 90 wt% to 100 wt%, or about 80 wt% to about 100 wt%, or about 90 wt% to about 99.5 wt%, or about 80 wt% to about 99.5 wt% esters, based on the weight of the second reaction product.

[0121] The second reaction product can individually contain 0 wt% to 1 wt%, or 0 wt% to 2 wt%, or 0 wt% to 3 wt%, or 0 wt% to 4 wt%, or 0 wt% to 0.1 wt%, or 0 wt% to 0.01 wt%, or 0 wt% of each of the following types of materials in total: abietic acid, salts of abietic acid, amides of abietic acid, esters of abietic acid, fatty acid esters, imidazolines, and C1-C10 monohydric alcohols, based on the weight of the second reaction product.

[0122] The second set of reactants may comprise, consist essentially of, or consist of one or more glycerol-restricted 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 include, consist essentially of, or consist of one or more of monoalkanolamines, dialkanolamines, and trialkanolamines. In some preferred embodiments and implementations herein, the one or more tertiary amines may comprise, consist essentially of, or consist of triethanolamine (TEA) ((HOCH2CH2)3N).

[0123] The one or more glycerol-restricted vegetable oil fatty acids of the second set may be the same as, substantially the same as, or different from those used to prepare the first reaction product as described with respect to Scheme 9, and may be selected from one or more of the following: glycerol-restricted avocado oil fatty acids, canola oil fatty acids, coconut oil fatty acids, corn oil fatty acids, cottonseed oil fatty acids, grapeseed oil fatty acids, hazelnut oil fatty acids, hempseed oil fatty acids, linseed oil fatty acids, olive oil fatty acids, palm oil fatty acids, palm kernel oil fatty acids, peanut 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 oil fatty acids, and walnut oil fatty acids.

[0124] In some preferred embodiments and implementations disclosed herein, the one or more glycerol-restricted vegetable oil fatty acids of the second set may comprise, consist essentially of, or consist of glycerol-restricted soybean oil fatty acids.

[0125] The second set of glycerol-restricted vegetable oil fatty acids may contain 0 wt% to 0.01 wt%, or 0 wt% to 0.02 wt%, or 0 wt% to 0.03 wt%, or 0 wt% to 0.05 wt%, or 0.05 wt% to 0.1 wt%, or about 0 wt% glycerol, based on the weight of the second set of glycerol-restricted vegetable oil fatty acids (including glycerol content, if any).

[0126] The third embodiment of the present invention

[0127] In a third implementation of the present invention, there is provided a concentrate that comprises any one of the additives of the first or second implementation of the present invention, and further comprises an organic solvent in which a plurality of amides, their ammonium salts, and / or a plurality of esters are dissolved, dispersed, or otherwise mixed with the organic solvent. The term "concentrate" is defined in the foregoing detailed description, and that definition applies to the third implementation of the present invention and any implementation in which one or more additives of the present invention are incorporated into a concentrate.

[0128] The organic solvent can be selected from a wide range of liquid carriers such as esters and / or hydrocarbons. The hydrocarbons can be selected from one or more of aromatic compounds, alkanes, any type of naphtha, and olefins. Examples of suitable hydrocarbons include, but are not limited to, benzene, toluene, xylene (ortho-xylene, meta-xylene, para-xylene, and any combination thereof), heavy aromatic naphtha (HAN), C5 to C17 alkanes, olefins, and naphtha, one or more of them. Examples of esters include, but are not limited to, phthalates such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, and combinations thereof. The solvent can include, consist of, or consist essentially of dimethyl phthalate.

[0129] The weight ratio of the organic solvent to the first reaction product, the second reaction product, or a combination of the first reaction product and the second reaction product 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.

[0130] The weight concentration of the first reaction product, the second reaction product, or a combination of the first reaction product and the second reaction product in the concentrate can be 50 wt% to 99 wt%, or 50 wt% to 90 wt%, or 50 wt% to 80 wt%, or 60 wt% to 90 wt%, or 60 wt% to 80 wt%, or 70 wt% to 90 wt%, or 70 wt% to 99 wt%, or about 80 wt% based on the weight of the concentrate.

[0131] The fourth embodiment of the present invention

[0132] In a fourth embodiment of the present invention, an additive is provided that comprises, consists of, or consists essentially of one or more ammonium salts of any of the glycerol-restricted amides described above in the first embodiment of the present invention. The ammonium salts can be prepared by reacting a component containing a plurality of amides with one or more of inorganic acids, organic acids, alkyl halides, and aryl halides. The resulting ammonium salts can optionally be incorporated into additive compositions such as corrosion inhibitor compositions in combination with one or more glycerol-restricted amides, one or more glycerol-restricted esters described in the second embodiment, an optional solvent, an optional one or more additional optional components, and combinations thereof.

[0133] The inorganic acid can comprise, consist of, or consist essentially of hydrochloric acid. The organic acids can include, consist of, or consist essentially of one or more of acetic acid, acrylic acid, and methacrylic acid. The alkyl halide can comprise, consist of, or consist essentially of alkyl chlorides. The aryl halide can comprise, consist of, or consist essentially of aryl chlorides.

[0134] In an exemplary embodiment, the polyglycerol-restricted amides include amides, each amide having the structure R-(CO)-(NH)-(CH2CH2NH)xCH2CH2NH2, where R is a hydrocarbon group and x is from 0 to 100. The amides react with and dissolve in acids such as HY, H2Y, H3Y, etc. (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 dissociates at least partially in water at 25 °C and 1 atmosphere of pressure to provide an aqueous composition having a pH of less than 7, even less than 5, even less than 4, or even less than 3, and where the reaction in the case of acid HY can be represented as shown in Scheme 11 below:

[0135] Solution 11

[0136] R-(CO)-(NH)-(CH2CH2NH)xCH2CH2NH2 + (x + 1)HY(aqueous solution) → [R-(CO)-(NH)-(CH2CH2NH2 + )xCH2CH2NH3 + Y (x+1) (aqueous solution)

[0137] Generally, the reaction between the acid and the polyamides can be summarized as:

[0138] Solution 12

[0139] Polyglyceryl amides + acid (aqueous solution) → polyammonium salts (aqueous solution)

[0140] Similarly, one or more amino groups in the polyamides can be converted to alkyl or aryl ammonium groups.

[0141] In a purely exemplary embodiment, the polyamides include amides having the structure R 1 -(CO)-(NH)-(CH2CH2NH)xCH2CH2NH2, where R 1 is a hydrocarbon group and x is from 0 to 100. The amides react with alkyl halides such as alkyl halides having the formula R 2 X, where one or more amino groups on the amide are converted to ammonium salts, where R 2 is a hydrocarbon group containing from 1 to 50 carbon atoms and X is a halide such as Cl and / or F. In a purely exemplary scenario, all or part of the amino -NH groups are converted to quaternary ammonium groups:

[0142] Solution 13

[0143] R-(CO)-(NH)-(CH2CH2NH)xCH2CH2NH2+(2x+3)R 2 Cl(aqueous solution) → [R-(CO)-(NH)-(CH2CH2NR 2 2 + )xCH2CH2NR 2 3 + Cl (x+1) (aqueous solution)+(x+2)HCl

[0144] Generally speaking, the reaction between alkyl halides and various amides can be summarized as follows:

[0145] Solution 14

[0146] Various amides + alkyl halides → various alkyl ammonium salts

[0147] Although additives containing amides, consisting of or substantially consisting of amides are particularly useful as, for example, corrosion inhibition additives for hydrocarbon process streams, the ammonium salts disclosed herein are particularly useful as additives for aqueous process streams, such as aqueous corrosion inhibitors.

[0148] Any one of the additives and concentrates or other compositions of the first, second, third, or fourth embodiments of the present invention may include one or more optional components, such as one or more anti - polymerizers, antioxidants, and amines, or other optional components discussed in other aspects as described herein.

[0149] The fifth embodiment of the present invention

[0150] In a fifth embodiment of the present invention, a method for preparing the first additive as described above with respect to Scheme 4a, Scheme 4b, and Scheme 9 is provided. The method includes: (1) combining one or more glycerol - restricted vegetable oil fatty acids with a polyamine to form a reaction mixture. The one or more glycerol - restricted vegetable oil fatty acids may include one or more of the above - mentioned hydrolyzed vegetable oils that are at least partially purified relative to glycerol, consisting of or substantially consisting of the same. Optionally, the method further includes (2) adding a hydrocarbon solvent, for example, heavy aromatic naphtha (HAN), as a liquid carrier to the reaction mixture. Preferably, the hydrocarbon solvent has a boiling point of at least 160 °C at one atmosphere. However, the reaction can be carried out at a pressure above one atmosphere to increase the boiling point of the hydrocarbon solvent and reach the desired reaction temperature.

[0151] The molar ratio of one or more glycerol-restricted vegetable oil fatty acids to polyamine in the combined reaction mixture can be from 3:1 to 4:1, or from 3.4:1 to 3.7:1, or about 3.5:1 to 3.6:1. Although one or more glycerol-restricted vegetable oil fatty acids can be a complex mixture of fatty acids, for calculating the aforementioned molar ratio, the acid value of the free fatty acids can be used to calculate the molecular weight of the free fatty acids. If the polyamine is a mixture of individual polyamine compounds with various molecular weights, then for calculating the above molar ratio, the number average molecular weight of the polyamine can be used. However, if the polyamine is a discrete compound, such as tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2), then the molecular weight of the discrete compound is used.

[0152] The method further comprises (3) optionally heating the reaction mixture for a period of time in the range of 30 minutes to 20 hours, or 1 hour to 15 hours, or 1 hour to 10 hours, or 5 hours to 15 hours at a suitable reaction temperature, such as in the range of 150 °C to 200 °C, or 160 °C to 190 °C, or 160 °C to 175 °C, or 165 °C to 170 °C, under an inert gas such as nitrogen, argon, etc., to form a first reaction product and by-product water. Preferably, the reaction temperature does not exceed 200 °C to avoid forming an excessive amount of imidazoline as a by-product.

[0153] Preferably, the method further comprises (4) removing the by-product water from the reaction mixture during heating, for example, by trapping the water in a Dean-Stark water separator during heating. Removing water while heating the reactants helps to drive the reaction forward and produce the desired amide.

[0154] The sixth embodiment of the present invention

[0155] In a sixth embodiment of the present invention, there is provided a method for preparing a combined additive as described above in the second embodiment of the present invention. The method includes: (1) combining one or more glycerol-restricted vegetable oil fatty acids with a polyamine to form a first reaction mixture, optionally but preferably under conditions such that the temperature of the reaction mixture does not exceed 100 °C. The glycerol-restricted vegetable oil fatty acids may comprise, consist of, or consist essentially of one or more hydrolyzed vegetable oils that are at least partially purified relative to glycerol. The one or more glycerol-restricted vegetable oil fatty acids may comprise, consist of, or consist essentially of glycerol-restricted soybean oil fatty acids. The polyamine may comprise, consist of, or consist essentially of tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2) (TEPA). Optionally, the method further includes (2) adding a hydrocarbon solvent, for example, heavy aromatic naphtha (HAN), to the reaction mixture. Preferably, the hydrocarbon solvent has a boiling point of at least 160 °C at one atmosphere. However, the reaction may be carried out at a pressure above one atmosphere to increase the boiling point of the hydrocarbon solvent and reach the desired reaction temperature.

[0156] The molar ratio of the total glycerol-restricted vegetable oil fatty acids to the total polyamine in the reaction mixture may be from 3:1 to 4:1, or from 3.4:1 to 3.7:1, or about 3.5:1 to 3.6:1. Although the one or more glycerol-restricted vegetable oil fatty acids may be a mixture of fatty acids, for calculating the foregoing molar ratio, the acid value of the free fatty acids may be used to calculate the molecular weight of the free fatty acids. If the polyamine is a mixture of individual polyamine compounds having various molecular weights, for calculating the above molar ratio, the number average molecular weight of the polyamine may be used. However, if the polyamine is a discrete compound, such as tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2), the molecular weight of the discrete compound is used.

[0157] The method further includes (3) heating the reaction mixture for a period within the range of 30 minutes to 20 hours, or 1 hour to 15 hours, or 1 hour to 10 hours, or 5 hours to 15 hours at a reaction temperature within the range of 150 °C to 200 °C, or 160 °C to 190 °C, or 160 °C to 175 °C, or 165 °C to 170 °C, optionally under an inert gas such as nitrogen, argon, etc., to form a first reaction product comprising water and a first additive. Preferably, the reaction temperature does not exceed 200 °C to avoid forming an excessive amount of imidazoline as a by-product.

[0158] Preferably, the method further includes (4) removing water from the reaction mixture during heating, for example, by trapping water in a Dean-Stark water separator during heating.

[0159] The method further comprises (5) combining one or more second glycerol-restricted vegetable oil fatty acids with one or more tertiary amines, each of the one or more tertiary amines comprising at least one hydroxyl group, to form a second reaction mixture; and (6) optionally heating the second reaction mixture at a reaction temperature in the range of 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, under an inert gas such as nitrogen, for a period of 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.

[0160] One or more second glycerol-restricted vegetable oil fatty acids may comprise, consist of, or consist essentially of a hydrolyzed vegetable oil at least partially purified relative to glycerol as described herein. One or more second glycerol-restricted vegetable oil fatty acids may comprise, consist of, or consist essentially of glycerol-restricted soybean oil fatty acids. One or more tertiary amines may include, consist of, or consist essentially of triethanolamine.

[0161] The molar ratio of one or more second glycerol-restricted vegetable oil fatty acids to one or more tertiary amines in the second reaction mixture may be selected from a wide range such as 1:1 to 2:1, or 1.5:1 to 1.7:1, or about 1.6:1. Although one or more glycerol-restricted vegetable oil fatty acids comprise a mixture of fatty acids, for calculating the foregoing molar ratio, the acid value of the one or more glycerol-restricted vegetable oil fatty acids may be used to calculate the molecular weight.

[0162] Optionally, the method for preparing the combined additive further comprises (7) adding a hydrocarbon solvent, e.g., heavy aromatic naphtha (HAN), to the second reaction mixture before, after, or during the heating of the second reaction mixture.

[0163] Preferably, the method further comprises (8) removing water from the second reaction mixture during its heating, e.g., by trapping water in a Dean-Stark water separator during the heating.

[0164] The method for preparing the combined additive further comprises combining the first reaction product with the second reaction product to form a combined additive. The weight ratio of the total amide to the total ester content in the combined additive may be selected from a wide range, such as 50:1 to 1:50, 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.

[0165] Any one of the first additive, the second additive, and / or the combined additive disclosed herein can be added to a hydrocarbon composition comprising one or more hydrocarbons to provide a treated hydrocarbon composition.

[0166] The seventh embodiment of the present invention

[0167] Accordingly, in a seventh embodiment of the present invention, a method for inhibiting corrosion of a surface in contact with a hydrocarbon composition is provided, the method comprising combining, consisting of, or consisting essentially of the hydrocarbon composition with any one or more of the first, second, and / or combined additive compositions disclosed herein.

[0168] The surface can 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.

[0169] The additive can be added to a batch or process stream of the hydrocarbon composition in a wide range of amounts, such as from 1 to 24 parts by weight of one or more additives per million parts by weight (ppm) of the hydrocarbon composition, or from 2 ppm to 9 ppm, or from 0.1 ppm to 1000 ppm, or from 0.5 ppm to 100 ppm, or from 0.5 ppm to 50 ppm, or from 0.1 ppm to 10000 ppm by weight of one or more additives.

[0170] The hydrocarbon composition can be a process stream comprising, consisting of, or consisting essentially of one or more hydrocarbons; or a batch of hydrocarbon composition comprising, consisting of, or consisting essentially of one or more hydrocarbons. The hydrocarbon composition can comprise, consist of, or consist essentially of one or more of crude oil, refined petroleum, cracked petroleum, hydrotreated process stream, liquid ethylene, liquid methane, and naphtha.

[0171] An additive composition comprising a plurality of amides, an additive composition comprising a plurality of esters, and the combined additive composition described herein can be added to the hydrocarbon composition to provide protection against corrosion of a surface in contact with the hydrocarbon composition and / or a hydrocarbon process stream (such as a carbon steel surface). Corrosion agents commonly found in hydrocarbon compositions derived from crude oil are naphthenic acid and / or its salts. Accordingly, in any of the embodiments described herein, the hydrocarbon composition or process stream can comprise naphthenic acid. The additives in the additive composition provide corrosion protection, but can also provide protection against deposits and / or precipitation by acting as a dispersant.

[0172] The hydrocarbon composition may comprise one or more corrosives selected from naphthenic acid and / or its salts, water, brine, organic chlorides, inorganic chlorides, hydrogen sulfide, organic sulfur compounds, carbon dioxide, dissolved oxygen, 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 methanethiol, ethanethiol, and propanethiol. The hydrocarbon composition comprising any one or more corrosives may be in contact with metal components and / or vessels and may cause their corrosion. The addition of the additives disclosed herein inhibits such corrosion. In other words, when the disclosed additives are added to a hydrocarbon composition comprising one or more corrosives, the corrosion of surfaces such as carbon steel surfaces in contact with the treated process stream appears to be delayed. Without being bound by theory, we speculate that the additives temporarily or permanently modify the metal surfaces that are in contact with or have been contacted by the additives. Alternatively, the additives may inhibit the effects of the corrosives in the oil in some way. Regardless of the mechanism, when added to a hydrocarbon composition in contact with corrodible metal components, the additives impart corrosion protection.

[0173] Any one of the additives, reaction products, polyamides, and polyesters described herein may be used in compositions and methods in downstream oil processes in the manner described, for example, in U.S. Patent 3,766,053, which is incorporated herein by reference in its entirety and for all purposes.

[0174] The eighth embodiment of the present invention

[0175] Accordingly, in an eighth embodiment of the present invention, there is provided a treated hydrocarbon composition comprising any one of the hydrocarbon compositions disclosed herein and any one or more, consisting of, or consisting essentially of the additive compositions, reaction products, polyamides, polyesters, and combinations thereof described herein. Prior to the addition of the additive, the hydrocarbon composition comprises one or more hydrocarbons, consists of, or consists essentially of the same.

[0176] The ratio of the weight of the additive composition, reaction product, polyamide, polyester, and combinations thereof to the weight of the treated hydrocarbon composition may be from 1 part per million (ppm) to 24 ppm by weight, or from 2 ppm to 9 ppm, or from 0.1 ppm to 1000 ppm, or from 0.5 ppm to 100 ppm, or from 0.5 ppm to 50 ppm, or from 0.1 ppm to 10000 ppm by weight.

[0177] Any one of the additive compositions, reaction products, various amides, various esters, and combinations thereof described herein may separately contain from 0 wt% to 5 wt%, or from 0 wt% to 4 wt%, or from 0 wt% to 3 wt%, or from 0 wt% to 2 wt%, or from 0 wt% to 1 wt%, or from 0 wt% to 0.1 wt%, or from 0 wt% to 0.01 wt%, or 0 wt%, or from 0.0001 wt% to 0.1 wt% of glycerol, based on the weight of the additive composition, reaction product, various amides, various esters, and combinations thereof.

[0178] Any one of the additive compositions, reaction products, various amides, various esters, and combinations thereof described herein may separately contain from 0 wt% to 4 wt%, or from 0 wt% to 3 wt%, or from 0 wt% to 2 wt%, or from 0 wt% to 1 wt%, or from 0 wt% to 0.1 wt%, or from 0 wt% to 0.01 wt%, or 0 wt%, or from 0.0001 wt% to 0.1 wt% of total rosin, total resin acids, total resin acid derivatives, or any combination thereof, based on the weight of the additive composition, reaction product, various amides, various esters, and combinations thereof.

[0179] Example

[0180] 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 present invention. It should be recognized that various modifications and changes can be made without departing from the scope of the claims.

[0181] Example 1: Synthesis of SOFA-TEPA amide from glycerol-restricted soybean oil fatty acids obtained from Supplier A

[0182] To a 250 mL four-neck round-bottom flask equipped with a temperature probe, a nitrogen inlet, a Dean-Stark apparatus, a condenser, and a magnetic stir bar was added glycerol-restricted soybean oil fatty acids (89.6 g) obtained from a first supplier (Supplier A). Next, tetraethylenepentamine (17.1 g, 0.090 moles) was added to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to rise from 21 °C to approximately 44 °C. Then heavy aromatic naphtha (18.3 g) was added to the well-stirred reaction mixture. Nitrogen purging 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 the liquid collected in the Dean-Stark water separator 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.

[0183] Example 2: Synthesis of SOFA-TEPA amide from glycerol-restricted soybean oil fatty acids obtained from Supplier B

[0184] To a 250 mL four-necked round-bottom flask equipped with a temperature probe, a nitrogen inlet, a Dean-Stark apparatus, a condenser, and a magnetic stir bar was added glycerol-restricted soybean fatty acid (72.73 g) obtained from a second supplier (Supplier B). Subsequently, tetraethylenepentamine (13.68 g, 0.072 mole) was added to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to rise from 21 °C to approximately 61 °C. Then heavy aromatic naphtha (HAN) (13.59 g) was added to the well-stirred reaction mixture. Nitrogen purging was initiated, and the reaction was heated to approximately 170 °C and maintained 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 the liquid collected in the Dean-Stark water separator 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.

[0185] Example 3: Synthesis of SOFA-TEA ester from glycerol-restricted soybean oil fatty acids obtained from Supplier A

[0186] To a 250 mL four-necked round-bottom flask equipped with a temperature probe, a nitrogen inlet, a Dean-Stark apparatus, a condenser, and a magnetic stir bar was added glycerol-restricted soybean fatty acid (44.97 g) obtained from Supplier A. Subsequently, triethanolamine (15.75 g, 0.10 mole) was added to the well-stirred reaction mixture. The reaction was heated to approximately 210 °C and maintained 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 cooled to room temperature. The product remained a clear liquid and showed no signs of phase separation over time.

[0187] Example 4: Synthesis of SOFA-TEA ester from glycerol-restricted soybean oil fatty acids obtained from Supplier B

[0188] To a 250 mL four-necked round-bottom flask equipped with a temperature probe, a nitrogen inlet, a Dean-Stark apparatus, a condenser, and a magnetic stir bar was added glycerol-restricted soybean fatty acid (45.65 g) obtained from Supplier B. Subsequently, triethanolamine (15.75 g, 0.10 mole) was added to the well-stirred reaction mixture. The reaction was heated to approximately 210 °C and maintained at that temperature for approximately 4 hours. The reaction was cooled to less than 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 cooled to room temperature. The product remained a clear liquid and showed no signs of phase separation over time.

[0189] Example 5: Additive from soybean oil

[0190] To a 1 L four-necked round-bottom flask equipped with a temperature probe, a nitrogen inlet, a Dean-Stark apparatus, a condenser, and a magnetic stir bar, 343.5 g of soybean oil and a few drops (0.01 g) of antifoam silicone were added. The flask and its contents were heated to 80 °C under a nitrogen purge, and diethylenetriamine (129.99 g, 1.26 moles) was added slowly so that the contents of the flask did not exceed 100 °C and foaming was avoided. After the addition was complete, the contents of the flask were heated at 165 °C for 1 hour to form an amide, and the formation of the amide in the reaction mixture was monitored by taking small samples and examining them by infrared spectroscopy for the disappearance of the peak associated with the ester carbonyl at 1742 cm- 1 and the appearance of the peak associated with the amide carbonyl at 1645 cm -1 .

[0191] The contents of the reaction flask were then heated to 245 °C for 3 hours to cyclize the amide to imidazoline. The formation of imidazoline in the reaction was monitored by taking small samples and examining them by infrared spectroscopy for the disappearance of the amide carbonyl peak at 1645 cm- 1 and the appearance of the imine peak at 1602 cm -1 .

[0192] The contents of the reaction vessel were cooled and transferred to a wide-mouth bottle. Immediately after the transfer, the contents of the wide-mouth bottle were a clear liquid, but after three days, the contents of the wide-mouth bottle were turbid and phase-separated into layers.

[0193] Example 6: Additive from glycerol-restricted soybean oil fatty acids

[0194] To a 250 mL four-necked round-bottom flask equipped with a temperature probe, a nitrogen inlet, a Dean-Stark apparatus, a condenser, and a magnetic stir bar, glycerol-restricted soybean oil fatty acids (70.99 g) were added. Next, 2-aminoethylethanolamine (29.00 g, 0.278 moles) was added to the well-stirred reaction mixture. The temperature of the contents of the flask rose from room temperature to a temperature between about 50 °C and about 60 °C. The viscous reaction mass was heated at about 180 °C for about 8 hours. Then the reaction mixture was heated to about 225 °C and held at that temperature for about 5 hours. About 4 mL to 5 mL of water was collected in the Dean-Stark water separator. The contents of the flask were cooled to below 100 °C and transferred to a wide-mouth bottle.

[0195] Samples of the reaction product SOFA-imidazoline were stored at -10 °C and no turbidity or precipitation occurred after 11 days and 3 months.

[0196] A sample (8 g) of the SOFA-imidazoline product was blended with dimethyl phthalate (2 g) to form a concentrate. The concentrate was stored at -10 °C and no turbidity or precipitation occurred after one week, 44 days, or even 95 days.

[0197] Example 7: Additive concentrate from tall oil fatty acids

[0198] The procedure of Example 6 was repeated, but using tall oil fatty acid instead of glycerol-restricted soybean oil fatty acid.

[0199] A sample of the reaction product TOFA-imidazoline was stored at -10 °C for 11 days and precipitation occurred.

[0200] A sample (8 g) of the TOFA-imidazoline product was blended with dimethyl phthalate (2 g) to form a concentrate. The concentrate was stored at -10 °C and precipitation occurred only after a few days. After storing at -10 °C for 64 days, the precipitate could not be easily redissolved.

[0201] Comparison with Example 6 shows that the SOFA-imidazoline additive is more stable than the corresponding TOFA-imidazoline additive when stored at low temperature, whether in 100% form or when formulated as a concentrate in an organic solvent (dimethyl phthalate).

[0202] Example 9: Synthesis of TOFA-TEPA amide from tall oil fatty acids

[0203] The synthesis steps of Examples 1 and 2 were repeated, except that tall oil fatty acid was used instead of glycerol-restricted soybean oil fatty acid.

[0204] Example 10: Synthesis of TOFA-TEA ester from tall oil fatty acids

[0205] The synthesis steps of Examples 3 and 4 were repeated, except that tall oil fatty acid was used instead of glycerol-restricted soybean oil fatty acid.

[0206] Example 11: Combined amide-ester corrosion inhibitor (CAE)

[0207] The TOFA-TEPA amide and TOFA-TEA ester prepared as in Example 9 and Example 10 respectively were mixed at a ratio of 1 part by weight of TOFA-TEPA amide to 3.5 parts by weight of TOFA-TEA ester to prepare CAE2.

[0208] The SOFA-TEPA amide and SOFA-TEPA ester prepared as in Examples 2 and 4 respectively were mixed at a ratio of 1 part by weight of SOFA-TEPA amide to 3.5 parts by weight of SOFA-TEA ester to prepare CAE3.

[0209] The SOFA-TEPA amide and SOFA-TEPA ester prepared as in Example 2 and Example 4 respectively were mixed at a ratio of 1 part by weight of SOFA-TEPA amide to 3.5 parts by weight of SOFA-TEA ester to prepare CAE4.

[0210] The SOFA-TEPA amide and SOFA-TEPA ester prepared as in Example 1 and Example 3 respectively were mixed at a ratio of 1 part by weight of SOFA-TEPA amide to 3.5 parts by weight of SOFA-TEA ester to prepare CAE5.

[0211] Example 12: Corrosion inhibitor performance through gearbox testing

[0212] A wheelbox test (NACE 1D182, "Wheelbox Test Method for Evaluating Membrane Persistent Corrosion Inhibitors for Oilfield Applications") was conducted to evaluate three different concentrations of each of CAE2 to CAE5 in the light fraction of the hydrotreating of oil. Another sample of crude oil without any amide-ester corrosion inhibitor combination, labeled here as CAE1, was also evaluated, as shown in Table 1. Multiple samples of each of CAE2 to CAE5 were evaluated.

[0213] The wheelbox test was carried out with brine (49.7 g / L of NH4C1 and 9.9 g / L of HCl in water), the gas was saturated H2S, the specimen was 1 / 4″ by 73 / 8″ 1018 mild steel with sandblasting treatment, the rotational speed of the wheel was 26 revolutions per minute (RPM), the test temperature was 160°F (71°C), and the test length was 24 hours. The corrosion inhibition results are also shown in Table 1.

[0214] Table 1: Corrosion inhibition samples

[0215]

[0216] Excellent corrosion protection results were obtained using the corrosion inhibitors CAE2, CAE3, CAE4, and CAE5.

Claims

1. An additive composition, the additive composition comprising a plurality of amides and / or their ammonium salts, wherein at least a portion of the plurality of amides comprises a reaction product derived from a first set of reactants, the first set of reactants comprising one or more first glycerol-restricted vegetable oil fatty acids and a polyamine, wherein the one or more first glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol, based on the weight of the one or more first glycerol-restricted vegetable oil fatty acids, and wherein the polyamine has the formula NH2(CH2CH2NH)xCH2CH2NH2, where x is from 0 to 100.

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

3. The additive composition according to claim 1 or claim 2, wherein the one or more first glycerol-restricted vegetable oil fatty acids include glycerol-restricted soybean oil fatty acids.

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

5. The additive composition according to claim 4, wherein the one or more tertiary amines include triethanolamine.

6. The additive composition according to claim 4 or claim 5, wherein the one or more second glycerol-restricted vegetable oil fatty acids include glycerol-restricted soybean oil fatty acids.

7. The additive composition according to any one of claims 1 to 6, wherein the one or more first glycerol-restricted vegetable oil fatty acids and the one or more second glycerol-restricted vegetable oil fatty acids consist of glycerol-restricted soybean oil fatty acids.

8. The additive composition according to any one of claims 1 to 7, wherein the additive composition comprises from 0 wt% to 0.1 wt% glycerol, based on the additive composition.

9. The additive composition according to any one of claims 1 to 8, wherein the polyamine includes tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2).

10. The additive composition according to any one of claims 1 to 9, wherein each of the one or more first glycerol-restricted vegetable oil fatty acids and the one or more second glycerol-restricted vegetable oil fatty acids independently comprises from about 2 wt% to about 15 wt% of alpha-linolenic acid, from about 46 wt% to about 56 wt% of linoleic acid, from about 17 wt% to about 28 wt% of oleic acid, from about 1 wt% to about 10 wt% of stearic acid, and from about 5 wt% to about 15 wt% of palmitic acid, based on the one or more first glycerol-restricted vegetable oil fatty acids and the one or more second glycerol-restricted vegetable oil fatty acids, respectively.

11. The additive composition according to any one of claims 1 to 10, wherein the additive composition comprises from 0 wt% to 5 wt% of total imidazoline content, from 0 wt% to 5% of abietic acid, from 0 wt% to 5 wt% of total abietic acid derivatives, from 0 wt% to 5 wt% of total C1-C10 monohydric alcohols, and from 0% to 5 wt% of total fatty acid ester content, based on the additive composition.

12. The additive composition according to any one of claims 1 to 11, wherein the additive composition comprises the plurality of amides and heavy aromatic naphtha.

13. An aqueous composition, the aqueous composition comprising: (i) The additive composition according to any one of claims 1 to 11, wherein the additive composition comprises the ammonium salts of the plurality of amides; and (ii) Water in an amount greater than 5 wt% based on the additive composition.

14. The aqueous composition according to claim 13, wherein the ammonium salts of the plurality of amides comprise at least a portion of the reaction product of reactants comprising (a) A plurality of amides, and (b) One or more of an acid, an alkyl halide, and an aryl halide.

15. A hydrocarbon composition, the hydrocarbon composition comprising: (a) One or more hydrocarbons; and (b) An additive composition selected from among an amide composition and an ester composition, wherein the amide composition comprises a plurality of amides, at least a portion of the plurality of amides comprising the reaction product of a first set of reactants comprising one or more first glycerol-restricted vegetable oil fatty acids and a polyamine, wherein the one or more first glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% of glycerol, based on the weight of the one or more first glycerol-restricted vegetable oil fatty acids, and wherein the polyamine has the formula NH2(CH2CH2NH) x CH2CH2NH2, where x is from 0 to 100, wherein the ester composition comprises a plurality of esters, at least a portion of the plurality of esters comprising the reaction product of a second set of reactants comprising one or more second glycerol-restricted vegetable oil fatty acids and one or more tertiary amines, each of the one or more tertiary amines having at least one hydroxyl group, wherein the one or more second glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% of glycerol, based on the weight of the one or more second glycerol-restricted vegetable oil fatty acids.

16. The hydrocarbon composition according to claim 15, wherein the one or more first glycerin-restricted vegetable oil fatty acids, the one or more second glycerin-restricted vegetable oil fatty acids, or both the one or more first glycerin-restricted vegetable oil fatty acids and the one or more second glycerin-restricted vegetable oil fatty acids comprise glycerin-restricted soybean oil fatty acids.

17. The hydrocarbon composition according to claim 15 or claim 16, wherein the one or more first glycerin-restricted vegetable oil fatty acids, the one or more second glycerin-restricted vegetable oil fatty acids, or both the one or more first glycerin-restricted vegetable oil fatty acids and the one or more second glycerin-restricted vegetable oil fatty acids independently further comprise one or more additional fatty acids.

18. The hydrocarbon composition according to any one of claims 15 to 17, wherein the hydrocarbon composition comprises less than 0.1% by weight of rosin.

19. The hydrocarbon composition according to any one of claims 15 to 18, wherein the hydrocarbon composition comprises 0% to 0.1% by weight of glycerol based on the hydrocarbon composition.

20. The hydrocarbon composition according to any one of claims 15 to 19, wherein each of the one or more first glycerin-restricted vegetable oil fatty acids and the one or more second glycerin-restricted vegetable oil fatty acids comprises from about 2% to about 15% by weight of α-linolenic acid, from about 46% to about 56% by weight of linoleic acid, from about 17% to about 28% by weight of oleic acid, from about 1% to about 10% by weight of stearic acid, and from about 5% to about 15% by weight of palmitic acid, based on the weight of the one or more first glycerin-restricted vegetable oil fatty acids and the one or more second glycerin-restricted vegetable oil fatty acids, respectively.

21. The hydrocarbon composition according to any one of claims 15 to 20, wherein the polyamine comprises tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2).

22. The hydrocarbon composition according to any one of claims 15 to 21, wherein the additive composition comprises the ester composition, and wherein the one or more tertiary amines comprise triethanolamine.

23. The hydrocarbon composition according to any one of claims 15 to 22, wherein the one or more hydrocarbons comprise crude oil, refined petroleum, cracked petroleum, or any combination thereof.

24. The hydrocarbon composition according to any one of claims 15 to 22, wherein the one or more hydrocarbons comprise a hydrotreated process stream, liquid ethylene, liquid methane, naphtha, or any combination thereof.

25. The hydrocarbon composition according to any one of claims 15 to 24, wherein the one or more hydrocarbons comprise one or more corrosives selected from organic chlorides, inorganic chlorides, hydrogen sulfide, organic sulfur compounds, carbon dioxide, dissolved oxygen, organic acids, sodium chloride, magnesium chloride, calcium chloride, and inorganic ammonium chloride.

26. The hydrocarbon composition according to any one of claims 15 to 25, wherein the one or more hydrocarbons comprise naphthenic acid.

27. The hydrocarbon composition according to any one of claims 15 to 26, wherein the hydrocarbon composition comprises the ester composition, and the ester composition comprises one or more of the following: one or more monoesters of triethanolamine, one or more diesters of triethanolamine, and one or more triesters of triethanolamine.

28. The hydrocarbon composition according to any one of claims 15 to 27, wherein the additive composition comprises from 0 wt% to 5 wt% total imidazoline content, from 0 wt% to 5 wt% rosin acid, from 0 wt% to 5 wt% total rosin acid derivatives, from 0 wt% to 5 wt% total C1-C10 monohydric alcohols, and from 0 wt% to 5 wt% total fatty acid ester content, based on the weight of the additive composition.

29. The hydrocarbon composition according to any one of claims 15 to 28, wherein the hydrocarbon composition comprises both the amide composition and the ester composition.

30. The hydrocarbon composition according to any one of claims 15 to 29, wherein the hydrocarbon composition comprises from 1 part by weight to 24 parts by weight of the additive composition per million parts by weight of the one or more hydrocarbons.

31. The hydrocarbon composition according to any one of claims 15 to 30, wherein the hydrocarbon composition comprises from 2 parts by weight to 9 parts by weight of the additive composition per million parts by weight of the one or more hydrocarbons.

32. A method for inhibiting corrosion of a surface in contact with one or more hydrocarbons, the method comprising combining an inhibitor composition with the one or more hydrocarbons, wherein the inhibitor composition comprises the additive composition according to any one of claims 1 to 12.

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

34. The method according to claim 32 or claim 33, wherein the one or more hydrocarbons include crude oil, refined petroleum, cracked petroleum, or any combination thereof.

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

36. The method according to any one of claims 32 to 35, wherein the one or more hydrocarbons comprise naphthenic acid.

37. The method according to any one of claims 32 to 36, wherein the one or more hydrocarbons comprise one or more corrosion agents selected from organic chlorides, inorganic chlorides, hydrogen sulfide, organic sulfur compounds, carbon dioxide, dissolved oxygen, organic acids, sodium chloride, magnesium chloride, calcium chloride, and inorganic ammonium chloride.

38. The method according to any one of claims 32 to 37, wherein the inhibitor composition is combined with the one or more hydrocarbons in an ethylene unit, a cracked gas unit, a dilution stream feed pump, a cracked gas compressor, a reboiler, or a process water stripper.

39. The method according to any one of claims 32 to 38, wherein the inhibitor composition further comprises one or more of an anti-polymerizing agent, an antioxidant, an amide, or any combination thereof.

40. A method for preparing an additive composition, the method comprising: (1) combining one or more first glycerol-restricted vegetable oil fatty acids with a polyamine to form a first reaction mixture, wherein the one or more first glycerol-restricted vegetable oil fatty acids comprise from 0 wt% to 0.1 wt% glycerol, based on the weight of the one or more first glycerol-restricted 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 from 150 °C to 200 °C for a period of between 30 minutes and 20 hours to form water and a first reaction product, the first reaction product comprising a plurality of amides.

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

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

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

44. The method according to any one of claims 40 to 43, wherein the reaction mixture is heated under nitrogen.

45. The method according to any one of claims 40 to 44, wherein the temperature of the first reaction mixture and the temperature of the first reaction product do not exceed 200 °C.

46. The method according to any one of claims 40 to 45, wherein the temperature of the reaction mixture does not exceed 100 °C during the combining.

47. The method according to any one of claims 40 to 46, wherein the one or more first glycerol-restricted vegetable oil fatty acids comprise glycerol-restricted soybean oil fatty acids and the polyamine comprises tetraethylenepentamine (H2NCH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2).

48. A method for preparing a combined additive composition, the method comprising the method according to any one of claims 40 to 47, and further comprising: (4) combining one or more second glycerol-restricted vegetable oil fatty acids with one or more tertiary amines to form a second reaction mixture, wherein the one or more second glycerol-restricted vegetable oil fatty acids comprise from 0% to 0.1 wt% glycerol, based on the weight of the one or more second glycerol-restricted vegetable oil fatty acids, and wherein each of the one or more tertiary amines comprises at least one hydroxyl group; and (5) heating the second reaction mixture at a reaction temperature of from 150 °C to 300 °C for a period of between 30 minutes and 10 hours to form water and a second reaction product, the second reaction product comprising a plurality of esters; and (6) Combine the components containing the first reaction product and the second reaction product to form the combined additive composition.

49. The method according to claim 48, wherein the one or more second glycerol-restricted vegetable oil fatty acids include glycerol-restricted soybean oil fatty acids, and the one or more tertiary amines include triethanolamine.

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

51. The method according to any one of claims 48 to 50, wherein a hydrocarbon solvent is added to the second reaction mixture before, after, during the heating of the second reaction mixture, or any combination thereof.

52. The method according to any one of claims 48 to 51, wherein the method includes removing water from the second reaction mixture during the heating of the second reaction mixture.

53. The method according to any one of claims 48 to 52, wherein the weight ratio of the plurality of amides to the plurality of esters in the combined additive composition is from 1:3 to 1:4.

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