Composition with Fatty Acid Derivatives and Use in Industrial Processes

The invention is directed towards compositions including fatty acid derivatives and use as dispersants or as components antifoulant or anticorrosion formulations, and their use in with industrial processing equipment subject to fouling, such as compressors.

There are many technical challenges in industrial processes that involve the preparation, treatment, processing, refinement, storage, and transport of hydrocarbon-based materials. These include, among other, preventing polymerization of materials in processed compositions (anti-fouling), preventing corrosion of metal surfaces of processing equipment (anti-corrosion), and preventing settling of undesirable particulate material in processed compositions (dispersion).

Corrosion of metal surfaces is a technical challenge in industrial systems including the oil and gas industry. Such systems can include “corrodents” such as salts, other dissolved solids, liquids, gases or combinations thereof that cause, accelerate, or promote corrosion of metal containments that contact the corrodents. These aggressive constituents can cause severe corrosion as evidenced by surface pitting, embrittlement, and general loss of metal. As a result, almost all operators in the oil and gas industry employ corrosion inhibitors to reduce corrosion in metal containments, which contact liquids containing corrodents.

Fouling, for example, can be caused by ethylenically unsaturated monomers, such as vinyl aromatic monomers like styrene, can be present in processing streams or in refined products made by various chemical industrial processes. However, these monomer types may undesirably polymerize through radical polymerization especially at elevated temperature. As a result, solid deposits of polymer can form on the surface of the process equipment during industrial manufacture, processing, handling, or storage. The resulting polymers can be problematic and lead to equipment “fouling” and product contamination. Accordingly, this can necessitate treating the apparatus to remove the polymer, or may necessitate processing steps to remove the polymer from compositions streams or stored compositions. These undesirable polymerization reactions result in a loss in production efficiency because they consume valuable reagents and additional steps may be required to clean equipment and/or to remove the undesired polymers. Undesired polymerization reactions are particularly problematic in compositions having vinyl aromatic monomers.

To minimize undesired polymerization reactions, compounds that act as antipolymerants are often added to process streams or stored compositions. However, these antipolymerants should be effective at conditions associated with the processing method, compatible with the processing stream and other reagents, and should also be safe

Fouling of compressors is a well-known problem in processes using them such as cracked gas compression systems in ethylene processes. Steam cracking of hydrocarbons accounts for virtually all of the ethylene produced worldwide. In the process of producing ethylene, small polymer amounts can form. These polymers are generally considered contaminants and are undesirable.

For example, in an ethylene plant, ethylene (CH2=CH2) is produced from naphtha or ethane gas. Multiple gas compressors and inter-coolers are present in an ethylene plant, which are used to compress the cracked gases produced from the furnace after ethylene formation. Compression of gas helps to make the gas transportable and refrigerable. During the compression stage of gases, there is possibility of fouling in the units predominantly due to free radical polymerization of reactive monomers such as styrene, Diels-Alder reaction products, and formation of coke due to continuous exposure to high temperatures in the compressors. The polymers foul machines by depositing on, for example, the internal surfaces of compressors and inter-coolers resulting in reduced efficiency of the process and in some cases blocking the flow path and stopping production and in severe cases, damaging parts.

The frequent fouling and the need to clean can be a burden to production and efficiency of the operations.

Traditionally, antifoulant compositions that include inhibitors, dispersants, and corrosion inhibitor components have been commercially available as mixtures that are added to prevent fouling in compressors. Materials that have been used in such antifoulant compositions include derivatives of tall oil fatty acids. However, it has been found that use of tall oil fatty acid derivatives is less than desirable because tall oil fatty acid is a constrained material and further, tall oil includes components that reduce the performance of an antifoulant composition.

Disclosed herein are compositions including fatty acid derivatives, as well as their use in industrial processes to control unwanted polymerization, unwanted corrosion, and/or unwanted settling of particulate materials during industrial processes. Compositions of the disclosure can include one or more antipolymerants, anticorrodents, or other compounds that provide a benefit in an industrial process. Desirably compositions of the disclosure can minimize or eliminate tall oil-derived components, while at the same time beneficially providing performance that is at least the same or even superior to compositions made using fatty acid derivatives made from tall oil fatty acids. Compositions of the disclosure can be used in processes and systems that experience problems related to polymer fouling as otherwise caused by the unwanted polymerization of reactive monomeric compounds in processing streams. Exemplary uses of the fatty acid derivatives are for ethylene production or treatment, such as processes that use compressor equipment or an inter cooler.

It has been discovered herein that certain types of fatty acid preparations can be used for forming fatty acid derivatives, such as fatty acids amide and fatty acid esters, that provide surprising beneficial performance properties to compositions that are used as antifoulants, anticorrodents, and/or dispersants. The compositions of the disclosure beneficially have: (a) low amounts of fatty acid derivatives made from saturated C16 and C18 fatty acids, (b) higher amounts of fatty acid derivatives made from partially unsaturated C18 fatty acids, or both (a) and (b). For example, for (a) the saturated C16 (C16:0) and C18 (C18:0) fatty acid derivatives are present in an amount of not more than 15% (wt) of total fatty acid derivatives, and (b) C18:1-, C18:2-, and C18:3-fatty acid derivatives are present in the mixture, and the amount of C18:3-fatty acid derivatives is less than 7% (wt) of total fatty acid derivatives. Also, the compositions have less than 2% (wt) of amide or ester derivatives of rosin acid of total fatty acid derivatives, and less than 5% (wt) of glycerol of total fatty acid derivatives.

In another embodiment the invention provides an antifoulant, antioxidant, or/and dispersant composition that includes a mixture of fatty acid derivatives, wherein the fatty acid derivatives comprise fatty acid amides, fatty acid esters, or both and wherein the fatty acid derivatives are prepared from a soybean oil fatty acid preparation, a canola oil fatty acid preparation, or a mixture thereof, and wherein the composition has less than 2% (wt) of amide or ester derivatives of resin acid of total fatty acid derivatives and less than 5% (wt) of glycerol of total fatty acid derivatives, and optionally an antifoulant, an antioxidant, or a combination thereof.

These compositions can minimize or even eliminate the tall oil component rosin acid, and derivatives thereof that would otherwise be made upon reaction to form the fatty acid ester and/or amide derivatives in the composition.

In the composition the fatty acids derivatives can include a fatty acid amide a fatty acid ester, or a combination thereof, the derivatives having a hydrocarbon portion with 16 or more carbon groups, an amide group or ester group, and a heteroatom portion with one or more heteroatoms selected from N, O, and S. The heteroatom portion in the fatty acid amide or the fatty acid ester can have a carbon to heteroatom ratio of 4:1 or less, 3.0:1 or less, or 2.0:1 or less. In some embodiments where a mixture of fatty acid amide and fatty acid esters are used, in the composition the fatty acid esters are present in an amount by weight that is greater than the fatty acid amides. Fatty acid derivatives of the disclosure can be made by reacting a starting fatty acid preparation as described herein with amine and/or hydroxyl-containing compounds such as polyamines (e.g., linear and branched polyalkylene polyamines, thiolated polyakyleneimines, hydroxylated polyakyleneimines), polyoxyalkylenes (e.g., aminated polyoxyalkylenes), polyols, alcohol amines, and thiolamines.

Accordingly, in one aspect, the invention provides an antifoulant, antioxidant, or/and dispersant composition that includes two or more fatty acid derivatives, wherein the fatty acid derivatives are selected from fatty acid amides and fatty acid esters. Embodiments of the invention also provide compositions including the fatty acid derivatives of the disclosure, such as stock or concentrated compositions including the fatty acid derivatives, as well as working compositions including the fatty acid derivatives. In some compositions, the fatty acid derivatives are present in an amount greater than any other component in the composition (e.g., greater than about 25% (wt), 40% (wt), or 55% (wt)), or in an amount greater that a total amount of all other components in the composition. One or more components can be included in the composition along with the fatty acid derivatives, such as antioxidant(s) (e.g., about 0.1% (wt) to about 25% (wt)), or antipolymerant(s) (e.g., about 0.1% (wt) to about 25% (wt)), a polar or non-polar solvent (e.g., glycol, aromatic naphtha, etc.).

Beneficially, compositions of the disclosure performed at least as well or better than compositions made using fatty acid derivatives made from tall oil fatty acids in the functional categories of emulsion resolution, gel formation prevention, dispersion, resistance to phase separation, storage stability, and corrosion inhibition.

In some aspects, the fatty derivatives can be used in a dispersant composition to provide dispersant properties, without any antipolymerant or an antioxidant, such as in a method of dispersing particulates in an industrial composition associated with the preparation, treatment, processing, refinement, storage, or transport of hydrocarbon-based materials. In other aspects, the fatty derivatives can be used in a composition with an antipolymerant, an antioxidant, or both, to provide antipolymerant properties, antioxidant properties, optionally in addition to dispersant properties, without any antipolymerant or an antioxidant, in an industrial composition associated with the preparation, treatment, processing, refinement, storage, or transport of hydrocarbon-based materials.

In another aspect, the invention provides a method for reducing or preventing corrosion of process equipment comprising using a composition comprising fatty acid derivatives having the features as described herein, wherein the composition reduces or prevents corrosion of the process equipment. For example, the fatty acid derivatives can be used as part of a composition that is used in conjunction with a method of ethylene production or treatment, such as one that uses compressor equipment or an inter cooler, in order to prevent corrosion of the surfaces of such equipment.

In another aspect, the invention provides a method dispersing particulates in a medium comprising adding a composition comprising fatty acid derivatives having the features as described herein, to a medium comprising or capable of forming particulates. For example, a composition with the fatty acid derivatives can be used in a process wherein particulates are prone to forming particulates, such as particulates of polymeric material formed by the polymerization of monomers, or in compositions already having amounts of particulates.

Although the present disclosure provides references to embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. Various embodiments will be described in detail with reference to the drawings, wherein like reference numerals represent like parts and assemblies throughout the several views. Reference to various embodiments does not limit the scope of the claims attached hereto. Additionally, any examples set forth in this specification are not intended to be limiting and merely set forth some of the many possible embodiments for the appended claims.

An “antifoulant” refers to a compound or composition that including a compound that hinders or prevents the formation of “foulants” including polymers, prepolymers, oligomers in an industrial process, in process equipment, or both. Formation of foulants in an industrial process can otherwise lead to deposition of the foulants on the process equipment and hinder proper functioning of the process equipment, and can reduce efficiency and yield of the industrial process. An antifoulant can reduce foulant polymer formation by hindering or preventing the formation of active radical polymerizable species leading to polymer foulant formation. The antifoulant can be an “antipolymerant,” which refers to stable free radicals that are efficient in capturing or scavenging carbon-centered radicals through coupling reactions.

As used herein, the term “antioxidant” refers to compound(s) capable of scavenging oxygen-centered radicals through donating a hydrogen radical (H) to the oxygen-centered radicals.

As used herein, the term “process equipment” refers to apparatus that is used in a processing method, such as the production and/or refinement of chemical compounds. Examples of process equipment include compressors, fans, impellers, pumps, valves, inter-coolers, sensors, and the like. Process equipment can be in contact with a processed chemical composition and can be subject to fouling by deposition of polymeric materials on its surface. This term also includes sets of components which are in communication such as, for example, a series or “train” of gas compressors in an ethylene cracking process.

As used herein, the term “optional” or “optionally” means that the subsequently described object (e.g., compound), event (e.g., processing step), or circumstance may, but need not occur, and that the description includes instances where the object, event, or circumstance occurs and instances in which it does not.

As used herein, the term “about” modifying, for example, the quantity of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity that can occur, for example, through typical measuring and handling procedures used for making compounds, compositions, concentrates or use formulations; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods, and like proximate considerations. The term “about” also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture. Where modified by the term “about” the claims appended hereto include equivalents to these quantities. Further, where “about” is employed to describe any range of values, for example “about 1 to 5” the recitation means “1 to 5” and “about 1 to about 5” and “1 to about 5” and “about 1 to 5” unless specifically limited by context.

The disclosure provides certain fatty acid derivatives, such as fatty acids amide and fatty acid esters, that provide surprising beneficial performance properties to compositions that are used as antifoulants, anticorrodents, and/or dispersants. In some embodiments, the compositions of the disclosure have: (a) a low amount or no resin acid, (b) a very low amount or no glycerol, and (c) either (i) low amounts of C16:0- and C18:0-fatty acid derivatives, (ii) the presence of C18 partial unsaturated derivative (C18:1-, C18:2-, and C18:3-fatty acid derivatives) with C18:3-fatty acid derivatives in proportionally lower amounts, or (iii) both (i) and (ii). The fatty acid derivative can be used in compositions and methods to control unwanted polymerization, unwanted corrosion, and/or unwanted settling of particulate materials during industrial processes. Also, composition of the disclosure can minimize or eliminate tall oil derived components, while at the same time beneficially providing performance that is at least the same or even superior to compositions made using dispersant components derived from tall oil. Exemplary uses of the fatty acid derivatives are for ethylene production or treatment, such as processes that use compressor equipment or an inter cooler.

The fatty acid derivatives of the disclosure, such as fatty acid amides or fatty acid esters, can be prepared using a selected fatty acid composition. The selected fatty acid composition can be referred to as a “fatty acid starting composition” or a “fatty acid reactant composition” because it subsequently reacted with an amine group-containing or hydroxy-group-containing reactant. The fatty acid starting composition includes a mixture of fatty acids, and has one or more particular features pertaining to the types and/or amounts of certain fatty acids that are present in the mixture that, when formed into the fatty acid derivatives, provides advantages for use in industrial processes and methods, such as dispersant properties and/or antifoulant properties, as well as advantages for the storage of compositions that include these fatty acid derivatives. The fatty acid starting composition also has reduced, minimized, or essentially undetectable amounts of certain components, such as resin acids and glycerol, that can be otherwise found in some plant vegetable oil preparations. The starting fatty acid compositions of the disclosure can be obtained from commercial sources, can be prepared by refining crude fatty acid compositions to have specifications according to those of the disclosure, or can be formed from combining certain fatty acid preparation to meet such specifications.

Fatty acid compositions can be described in terms of various properties, including acid value, iodine value, titer (° C.), Gardner color, and percentage of particular fatty acids in the composition, including but not limited to the percentages of C16:0, C16:1, C18:0, C18:1, C18:2, C18:3, C20:0, C20:1, and C20:2 fatty acids. Acid value (AV) is commonly used to define the specifications of fats and oils, and is defined as the weight amount of KOH (mg) needed to neutralize the organic acids present in 1 g of fatty acid compositions, which provides a measure of the free fatty acids in the fatty acid composition. Typical acid values of fatty acid preparation are in the range of about 190-210, and fatty acid reactant composition of the used for preparation of the derivatives of the disclosure have an acid value in the range. Iodine value (IV) is commonly used to define the specifications of fats and oils, and is defined by the weight amount of iodine (g) consumed by 100 grams of a fatty acid or oil due to high reactivity of iodine (a halogen) with double bonds present in the fatty acid acyl chains. Iodine values reflect the degree of unsaturation in fatty acids, and the higher iodine values correlate with higher degrees of unsaturation in the fatty acid composition. The titer of a fatty acid composition is the temperature (degrees Celsius), at which the composition solidifies. Fatty acid compositions with higher degrees of saturation typically have lower titers.

Table 1 provides a list of certain saturated and partially unsaturated fatty acid can be found in plant fatty acid preparations.

Palmitic acid (C16:0) and stearic acid (C18:0) are also referred to herein as “C16 and C18 saturates.” As used herein “C16:1 fatty acids” and “C16:1 fatty acid derivatives” include palmitoleic acid and sapienic acid and derivatives thereof; “C18:1 fatty acids” and “C18:1 fatty acid derivatives” include oleic acid, elaidic acid, vaccenic acid and derivatives thereof; “C18:2 fatty acids” and “C18:2 fatty acid derivatives” include linoleic acid and linoelaidic acid and derivatives thereof. C18:1, C18:2, and C18:3 fatty acids are also referred to herein as “C18 partial unsaturates”. The compositions of the disclosure can also be described in some aspects with regards to amounts or ration of specific fatty acid species or derivatives thereof, such as amounts or rations of oleic acid and derivatives thereof in the composition, or amounts or rations of linoleic acid and derivatives thereof in the composition.

In particular the fatty acid starting composition has one or more of the following properties: (i) saturated C16 (C16:0) and C18 (C18:0) fatty acid are present in an amount of not more than 15% (wt) of total fatty acids in the starting composition; (ii) C18:1-, C18:2-, and C18:3-fatty acid derivatives are present in the mixture, and the amount of C18:3-fatty acid derivatives is less than 15% (wt) of total fatty acid derivatives or (iii) both (i) and (ii). Also, the fatty acids starting composition has less than 2% (wt) rosin acid, and preferably less than 1.5% (wt) rosin acid, less than 1% (wt) rosin acid, or less than 0.5% (wt) rosin acid. Also, the fatty acids starting composition has low amounts of glycerol, in particular less than 5% (wt) glycerol, and preferably less than 2.0% (wt), less than 1.5% (wt), less than 1% (wt), or less than 0.5% (wt) glycerol.

For example, in some fatty acid starting compositions, the (a) saturated C16 (C16:0) and C18 (C18:0) fatty acids can be present in an amount of not more than not more than 15% (wt), not more than 14% (wt), not more than 13% (wt), not more than 12% (wt), not more than 11% (wt), not more than 10% (wt), not more than 9% (wt), not more than 8% (wt), not more than 7% (wt), not more than 6% (wt), not more than 5.5% (wt), not more than 5.3% (wt), not more than 5.1% (wt), not more than 4.9% (wt), not more than 4.7% (wt), not more than 4.5% (wt), not more than 4.3% (wt), not more than 4.1% (wt), not more than 3.9% (wt), not more than 3.7% (wt), not more than 3.5% (wt), not more than 3.3% (wt), not more than 3.1% (wt), not more than 2.9% (wt), not more than 2.7% (wt), not more than 2.5% (wt), not more than 2.3% (wt), not more than 2.1% (wt), not more than 1.9% (wt), not more than 1.7% (wt), not more than 1.5% (wt), or not more than 1.3% (wt) of total fatty acid derivatives. In some embodiments, saturated C16 (C16:0) and C18 (C18:0) fatty acids may not be present in any detectable amount in the starting composition. However, if they are present, they can be in very small amounts such down to 0.1% (wt), 0.05% (wt), or 0.025% (wt), or an amount in the range of any of the lower and upper amounts described herein, such as an amount in the range of 0.025% (wt) to 14% (wt), 0.025% (wt) to 8% (wt), 0.025% (wt) to 5.5% (wt), 0.025% (wt) to 3.0% (wt), etc.

As another example, in some embodiments, C18:1-, C18:2-, and C18:3-fatty acids are all present in the starting composition. The combined amount of C18:1-, C18:2-, and C18:3-fatty acids can represent the majority of the total fatty acids or solids material in the starting fatty acid composition (i.e., greater than 50% on a weight basis). In some aspects, the C18:1, C18:2-, and C18:3-fatty acids are present in the mixture in a combined amount of: 60% (wt) or greater, 65% (wt) or greater, 70% (wt) or greater, 75% (wt) or greater, 80% (wt) or greater, 82.5% (wt) or greater, 85% (wt) or greater, or 87.5% (wt) or greater of total fatty acids or solids material in the starting fatty acid composition. For example, the C18:1-, C18:2-, and C18:3-fatty acids are present in the mixture in a combined amount in the range of 60%-97.5% (wt), 70%-95% (wt), 82.5%-95% (wt), or 85%-92.5% (wt) of total fatty acids in the starting composition.

The C18:1-, C18:2-, and C18:3-fatty acids can also be described individually in relation to the total amount of fatty acids or solids in the starting composition, or can be described individually in relation to one another. For example, in some embodiments, C18:1-fatty acid is present in the starting fatty acid composition in an amount of: at least 25% (wt), or at least 27.5% (wt); or an amount in the range of: 25%-75% (wt), 25%-70% (wt), or 25%-65% (wt), of total fatty acids in the starting composition.

In other embodiment, partially unsaturated C18:2 fatty acids (e.g., linoleic acid) are present in the starting composition in an amount of at least 20% (wt), at least 25% (wt), at least 30% (wt), at least 35% (wt), at least 40% (wt), at least 45% (wt), at least 50% (wt), or at least 55% (wt) of total fatty acids. The partially unsaturated C18:2 fatty acids can be present in amounts up to 99% (wt), up to 95% (wt), up to 90% (wt), up to 85% (wt), up to 80% (wt), or an amount in the range of any of the lower and upper amounts described herein, such as 20% (wt)-99% (wt), 25% (wt)-up to 90% (wt), 30% (wt)-85% (wt), etc.

The composition can optionally be described with reference to ratios of C18:1-, C18:2-, and C18:3-fatty acids. For example, in some starting fatty acid compositions, the fatty acids have a C18:1 to C18:2 weight ratio of less than 1.3:1, of less than 1.2:1, of less than 1.1:1, of less than 1.0:1, of less than 0.9:1, of less than 0.8:1, of less than 0.7:1, of less than 0.6:1, or of less than 0.5:1. The fatty acids have a C18:1 to C18:2 weight ratio of greater than 1:100, greater than 1:50, greater than 1:25, or greater than 1:25, or an amount in the range of any of the lower and upper ratios described herein, such as in the range of 1:100 to 1.3:1, in the range of 1:50 to than 1.2:1, or in the range of 1:25 to 1.1:1.

Starting fatty acid compositions also have low amounts of, or no detectable amounts of, resin acids. Resin acids are fused polycyclic carboxylic acid compounds having a hydrophenanthracene core that include dehydroabietic acid, abietic acid, neoabietic acid, levopimaric acid, palustric acid, pimaric acid, isopimaric acid, sandaracopimaric acid. Exemplary resin acids are shown in. Resin acids are commonly found in oils from coniferous trees. For example, tall oil (also known as liquid rosin or tallol) is obtained as a by-product of the kraft process of wood pulp process manufacture using coniferous trees. Tall oil also includes fatty acids, including predominantly C18-partially unsaturated fatty acids, and can be distilled and further processed to increase the concentration of fatty acids. However, the processing typically carries over minor amounts of resin acids along with the fatty acids, such as in amounts in the range of 2-6% (wt). However, according to the disclosure, it has been found that at least one property of the fatty acid derivative composition, such as storage stability, antifoulant activity, anti-corrodent activity, and/or dispersion activity, can be improved by minimizing the amount of resin acid in the composition below 2% (wt). Processes for the separation of resin acids from fatty acids have been described (e.g., see Mahood, H. W. and Rogers, I. H. (1975) Separation of resin acids from fatty acids in relation to environmental studies. J Chromatogr. 109:281-286).

Since the resin acids have carboxylic acid groups and are reactive with the amine and/or hydroxyl group-containing reactants otherwise used to make the fatty acid derivatives, the presence of resin acids along with the fatty acids will result in the formation of resin acid derivatives, which is desirably minimized or eliminated.

Accordingly, the amount of resin acids in the starting fatty acid composition is less than 2% (wt), and preferably, less than 1.75% (wt), less than 1.5% (wt), less than 1.25% (wt), less than 1% (wt), less than 0.75% (wt), less than 0.5% (wt), less than 0.25% (wt), less than 0.1% (wt), less than 0.05% (wt), less than 0.01% (wt), less than 0.005% (wt), or less than 0.001% (wt) of rosin acid, or no detectable amount of rosin acid.

Glycerol is the process coproduct when fats and oils are converted to fatty acids (fat splitting) or fatty acid esters (transesterification). Fatty acids and glycerol are produced from fats and oils, wherein the fat or oil is hydrolyzed (“split”), generally by using heat and pressure in the presence of water, to break the ester bond between the acid portion and the alcohol portion of the fat or oil. Amounts of glycerol of up to about 10% (wt) are typically generated in a splitting process. According to the disclosure, glycerol is desirably reduced or eliminated from the starting fatty acid composition to improve the properties of the resulting composition that includes the fatty acid derivatives.

Fatty acid compositions, such as those derived from vegetable sources like soybean or canola, and that have low levels of glycerol (which are also referred to as “glycerol restricted”), can be prepared or can be obtained commercially. For example, a process of producing low glycerol fatty acid compositions can include providing a vegetable oil starting composition, such as soybean oil or canola oil, and then adding an alkali such as aqueous sodium hydroxide and/or aqueous potassium hydroxide to the oil to produce a mixture. The oil/alkali is then heated to a suitable temperature to a temperature in the range from 30° C. to 100° C., such as about 60° C., for a period of time in the range of one to 24 hours, such as about four hours, effective for the saponification of vegetable oil. During saponification hydrolysis of the vegetable oil produces fatty acid salts and glycerol. To generate free fatty acids from the fatty acid salts, the pH of the mixture is reduced by adding a mineral acid such as sulfuric acid, hydrochloric acid, or a combination thereof. The addition of the acid changes the pH of the composition to a pH in the range of 1-4, such as a pH of about 2. An aqueous phase of water, a salt of the mineral acid, and glycerol separates from the organic phase into a distinct layer, and the aqueous phase is separated from the organic phase. Subsequently, the organic phase may be dried. The organic phase can then be further purified by separation into fractions, each fraction characterized by having acid numbers in different ranges. Fatty acid preparations having low amounts of glycerol can be found in fraction(s) having an acid number of in the range of 170 to 230 mg KOH/g, 180 to 220 mg KOH/g, 190 to 210 mg KOH/g, or about 192 to 205 mg KOH/g. For example, the vegetable oil fatty acid with low or no glycerol content (“glycerol restricted vegetable oil fatty acid”) may comprise, consist of, or consist essentially of glycerol-restricted soybean oil fatty acid or glycerol-restricted canola oil fatty acid having an acid number of about 192 to about 205 mgKOH/g.

By restricting the amount of glycerol in the starting fatty acid composition, this in turn restricts the amount of glycerol in the fatty acid derivative compositions, which can improve the derivative compositions by making them more stable by preventing phase separation of components of the compositions. In addition, the restricting the amount of glycerol can make improve the storage stability of the fatty acid derivative compositions, such as when stored at temperatures around 0° C. or below, such as in the range of 0° C. to −10° C. Accordingly, antifoulant compositions, antioxidant composition, and/or dispersant compositions can have better efficacy if the amount of glycerol is kept low or eliminated. In other modes of practice, the formulations or one or more components thereof, may be processed to remove at least a portion of the glycerol content to thereby improve stability against phase separation.

Accordingly, the amount of glycerol in the starting fatty acid composition is less than less than 5% (wt), less than 4% (wt), less than 3% (wt), less than 2.5% (wt), less than 2% (wt), less than 1.75% (wt), less than 1.5% (wt), less than 1.25% (wt), less than 1% (wt), less than 0.75% (wt), less than 0.5% (wt), less than 0.25% (wt), less than 0.1% (wt), less than 0.05% (wt), less than 0.01% (wt), less than 0.005% (wt), or less than 0.001% (wt), or the starting fatty acid composition has no detectable amount of glycerol. For example, in some embodiments, the composition has no detectable amount of fatty acid as determined from an analytical testing method such as nuclear magnetic resonance (NMR) or infrared (IR) spectroscopy.

The fatty acid starting compositions of the disclosure can be obtained from a “single fatty acid preparation” which refers to a fatty acids composition that was prepared according to a defined process using a source vegetable oil material. Typically, a “single fatty acid preparation” is derived from a certain vegetable oil starting material, which is then processed according to a certain procedure to provide a fatty acid preparation having specified properties. In many cases single fatty acid preparation is derived from a vegetable oil like soybean oil or canola oil using certain processing conditions, and the resultant fatty acid composition has the desired features of low or no resin acid, and low or no glycerol content, low amounts of C16 and C18 saturates, and higher amounts of C18 partial unsaturates, according to the current disclosure. However, two or more fatty acid preparations can be combined to provide a fatty acid composition (for subsequent reaction with amine and/or hydroxyl-containing reactants) having the desired properties. For example, a tall oil fatty acid preparation having an unacceptable rosin acid level above 2% (wt), but otherwise desirable low levels of C16 and C18 saturates, and higher amounts of C18 partial unsaturates, can be mixed with a fatty acid preparation from a vegetable oil, such as canola or soybean, which has no resin acid content, to lower the overall resin acid level below 2% (wt), below 1% (wt), or below 0.5% (wt), but yet still to provide a low glycerol level, and also low levels of C16 and C18 saturates, and higher amounts of C18 partial unsaturates.

Compositions of the disclosure can also include fatty acid derivative compositions that are formed from mixtures of fatty acid derivatives from fatty acids obtained from two or more different plant sources. For example, compositions of the disclosure can include a mixture of fatty acid derivates prepared from canola fatty acids and fatty acid derivates prepared from soy fatty acids, and optionally fatty acid derivates prepared from fatty acids of a plant that is not canola or soy. In other embodiments, compositions of the disclosure can include a mixture of fatty acid derivates prepared from canola fatty acids and fatty acid derivates prepared a plant that is not canola or soy. In other embodiments, compositions of the disclosure can include a mixture of fatty acid derivates prepared from soy fatty acids and fatty acid derivates prepared a plant that is not canola or soy. For example, fatty acids can be obtained from seeds such as flaxseed, hempseed, pumpkin seed, and rapeseed; nuts such as walnuts, almonds, cashews, peanut; or from woody trees.

The fatty acid derivative composition can be prepared by reacting a fatty acid starting composition with one or more of an amine group-containing, hydroxy-group-containing, or thiol group-containing reactant. As noted herein, the starting fatty acid composition has (i) C16:0- and C18:0-fatty acids present in an amount of less than 15% (wt) of total fatty acid derivatives, (ii) C18:1-, C18:2-, and C18:3-fatty acids with the amount of C18:3-fatty acids less than 15% (wt) of total fatty acids, or (iii) both (i) and (ii). Also, the fatty acid composition has less than 2% (wt), less than 1% (wt), or less than 0.5% (wt) of resin acids of total fatty acids, and less than 5% (wt), less than 1% (wt), less than 0.01% (wt), or no detectable amount of glycerol of total fatty acid derivatives.

In a method of synthesis, the amine group-containing, hydroxy-group-containing, or thiol group-containing reactant reacts with the carboxylic acid group of the fatty acid to form a “fatty acid derivative” which is a compound derived from these two types of reactants. As a general matter, the fatty acid derivative includes (i) a hydrocarbon portion comprising 16 or more carbon groups, (ii) an amide group, ester, or thioester linking group, (iii) a heteroatom portion comprising one or more heteroatoms selected from N, O, and S. For example, the fatty acid derivatives are any one or more of the following formulas:

In each of Formulas Ia-Ic, R is a hydrocarbon group in the range of 16-24 carbon atoms optionally having at least one unsaturated (—C═C—) group and X is a heteroatom portion including comprising one or more heteroatoms selected from N, O, and S.