US20250340794A1

US20250340794A1 - Composition with fatty acid derivatives and use in industrial processes

Info

Publication number: US20250340794A1
Application number: US19/194,453
Authority: US
Inventors: Kameswara R. Vyakaranam; Ashish Dhawan; Bassam Kamal Alnasleh; Jonathan Masere; Ravindranath Mukkamala
Original assignee: Ecolab USA Inc
Current assignee: Ecolab USA Inc
Priority date: 2024-05-01
Filing date: 2025-04-30
Publication date: 2025-11-06
Also published as: WO2025231070A1

Abstract

Disclosed are compositions including fatty acid derivatives and methods using the compositions as dispersants, antifoulants, or both. The compositions can be used to prevent or reduce polymer formation and polymer deposition in equipment used in petrochemical processes. The fatty acid derivative compositions are prepared from fatty acid preparations have low amounts of, or no, resin acids and glycerol, and also have low amounts of C16:0- and C18:0-fatty acids, and high total amounts of C18 partially unsaturated fatty acids, and/or the fatty acid derivative compositions are prepared from soy fatty acids and/or canola fatty acids. 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, compositions of the disclosure have the additional benefit of prolonged storage stability.

Description

TECHNICAL FIELD

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.

BACKGROUND

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.

SUMMARY

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.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 are chemical structures of various resin acids.

FIG. 2 is a flow process diagram for an ethylene production process.

FIG. 3 is a graph of amount of accumulated foulant in the presence of a control and various fatty acid derivative dispersant formulations.

FIG. 4 is a graph of amount of accumulated foulant in the presence of a control and various fatty acid derivative dispersant formulations.

DETAILED DESCRIPTION

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.

TABLE 1

Common	Chemical
name	structure	C:D

Saturated fatty acids

Palmitic	CH₃(CH₂)₁₄COOH	16:0
acid
Stearic	CH₃(CH₂)₁₆COOH	18:0
acid
Arachidic	CH₃(CH₂)₁₈COOH	20:0
acid
Behenic	CH₃(CH₂)₂₀COOH	22:0
acid
Lignoceric	CH₃(CH₂)₂₂COOH	24:0
acid

Partially unsaturated fatty acids

Palmitoleic	CH₃(CH₂)₅CH═CH(CH₂)₇COOH	16:1
acid
Sapienic	CH₃(CH₂)₈CH═CH(CH₂)₄COOH	16:1
acid
Oleic	CH₃(CH₂)₇CH═CH(CH₂)₇COOH	18:1
acid
Elaidic	CH₃(CH₂)₇CH═CH(CH₂)₇COOH	18:1
acid
Vaccenic	CH₃(CH₂)₅CH═CH(CH₂)₉COOH	18:1
acid
Linoleic	CH₃(CH₂)₄CH═CHCH₂CH═CH—(CH₂)₇COOH	18:2
acid
Linoelaidic	CH₃(CH₂)₄CH═CHCH₂CH═CH—(CH₂)₇COOH	18:2
acid
α-Linolenic	CH₃CH₂CH═CHCH₂CH═CHCH₂—CH═CH(CH₂)₇COOH	18:3
acid
Arachidonic	CH₃(CH₂)₄CH═CHCH₂CH═CHCH₂—CH═CHCH₂CH═CH(CH₂)₃COOH	20:4
acid
Eicosapentaenoic	CH₃CH₂CH═CHCH₂CH═CHCH₂C—H═CHCH₂CH═CHCH₂CH═CH—(CH₂)₃COOH	20:5
acid
Erucic	CH₃(CH₂)₇CH═CH(CH₂)₁₁COOH	22:1
acid
Docosahexaenoic	CH₃CH₂CH═CHCH₂CH═CHCH₂C—H═CHCH₂CH═CHCH₂CH═CHCH₂C—H═CH(CH₂)₂COOH	22:6
acid

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 FIG. 1 . 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.
In some aspects the heteroatom portion has one or more heteroatoms selected from N, O, and S and has a carbon to heteroatom ratio of 4:1 or less, 3.5:1 or less, 3.0:1 or less, 2.5:1 or less, or 2.0:1 or less, such as in the range of 4:1 to 1:1, or 3:1 to 1.5:1. In some aspects the heteroatom portion has carbon atoms and one or more heteroatoms selected from N, O, and S, and a number of carbon atoms in the range of 1-24, 2-18, or 3-16. As an example, a heteroatom portion having 8 carbon atoms with a carbon to heteroatom ratio in the range of of 4:1 to 1:1, could have 2-8 heteroatoms (such as N, O, or S, or a mixture thereof).
Exemplary amine group-containing reactants for reaction with a starting fatty acid composition include linear and branched polyalkylene polyamines, aminated polyoxyalkylenes, and heterocyclic amines, such as those having a number of carbon atoms in the range of 1-24, 2-18, or 3-16. Exemplary species in include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-Aminoethylpiperazine (AEP), and low molecular weight branched polyethyleneamines (e.g., having a molecular weight of less than 5000, or less than 2500). Aminated polyoxyalkylenes include species such as polyoxyethylene-bis-amine, 2,2′-(ethylenedioxy)bis(ethylamine), 1,11-diamino-3,6,9-trioxaundecane, 1,8-diamino-3,6-dioxaoctane, and 4,7,10-trioxa-1,13-tridecanediamine. Other amine group containing reactants include cystamine (2,2′-dithiobisethanamine). Examples of heterocyclic amines include imidazoline, 2-aminoimidazole, and 1(3-aminopropyl) imidazole.
Exemplary hydroxyl group containing reactants can be selected from hydroxylated polyakyleneimines, polyoxyalkylenes, alcohol amines, such as those having a number of carbon atoms in the range of 1-24, 2-18, or 3-16. Exemplary hydroxylated polyakyleneimines include N-(hydroxyethyl) diethylenetriamine, N-(2-hydroxyethyl)ethylenediamine, N,N′-bis(2-hydroxyethyl)ethylenediamine, and N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine. Exemplary alcohol amines include, diethanolamine, dipropanolaime, triethanolamine, triisopropanolamine, 1-[N,N-bis(2-hydroxyethyl)amino]-2-propanol, and N-(3-aminopropyl) diethanolamine. Other hydroxyl group containing reactants include bis(2-hydroxyethyl) disulfide (2,2′-dithiodiethanol).
Fatty acid derivatives can be formed by reacting an amine group-containing reactant or hydroxyl group containing reactant with a desired fatty acid preparation having low or no glycerol and resin acids, low C16 and C18 saturates, and C18:1-, C18:2-, and C18:3-fatty acids. Generally, the fatty acid preparation is reacted with the amine group-containing reactant or hydroxyl group containing reactant at a mole to mole ratio of fatty acid to reactant in the range of about 1-4.5 mole fatty acid preparation to 1 mole of reactant. In some embodiments wherein an amine group-containing reactant, such as a polyalkylene polyamines like TEPA, is used, the fatty acid preparation is reacted with the amine group-containing reactant at a mole to mole ratio in the range of about 3.4-3.6 mole fatty acid preparation to 1 mole of amine group-containing reactant, or more preferably about 3.44-3.52 mole fatty acid preparation to 1 mole of reactant of amine group-containing reactant. In some embodiments wherein a hydroxyl group-containing reactant, such as an alcohol amine like TEA, is used, the fatty acid preparation is reacted with the hydroxyl group-containing reactant at a mole to mole ratio in the range of about 1.4-1.7 mole fatty acid preparation to 1 mole of amine group-containing reactant, or more preferably about 1.47-1.61 mole fatty acid preparation to 1 mol of reactant of hydroxyl group-containing reactant.
The reactants can optionally be dissolved in a solvent, such as heavy aromatic naphtha (HAN). Reaction can be performed at elevated temperatures such as in the range of about 150° C.-225° C., or 150° C.-200° C.
The composition can include blends of two or more fatty acid amide preparations, wherein different amine group-containing reactants are used to prepare the two different fatty acid amide preparations. In some embodiments, the resultant product composition can include a blend of two or more fatty acid amides in a mass ratio of about 10:1 to 1:10, or from about 1:1 to 1:10 or from about 1:1 to 1:2. For example, in some embodiments, the composition includes a (first) reaction product of a fatty acid composition with diethylenetriiamine (DETA), and a (second) reaction product a fatty acid composition with tetraethylpentamine (TEPA).
Reaction forms a mixture of fatty acid derivatives, wherein the fatty acid derivatives comprise fatty acid amides or fatty acid esters, depending on the reactant that is used. In the reaction product composition (i) C16:0- and C18:0-fatty acid derivatives are present in an amount of less than 15% (wt) of total fatty acid derivatives, (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. Also, the composition has less than 2% (wt), or less than 1% (wt) of amide or ester derivatives of resin acid of total fatty acid derivatives and less than 5% (wt), less than 0.1% (wt), or no detectable amount of glycerol of total fatty acid derivatives.
In some aspects, the C18:1-, C18:2-, and C18:3-fatty acid derivatives are present in the composition 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; or in an amount in the range of 60%-97.5% (wt), 70%-95% (wt), 82.5%-95% (wt), or 85%-92.5% (wt) of total fatty acid derivatives.
In some aspects, the C18:1-fatty acid derivatives are present in the 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 acid derivatives.
In some aspects, the C18:2-fatty acid derivatives are present 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, or an amount in the range of 20% (wt)-99% (wt), 25% (wt)-up to 90% (wt), or 30% (wt)-85% (wt) of total fatty acid derivatives.
In some aspects, the composition has a weight ratio of C18:1-fatty acid derivatives to C18:2-fatty acid derivatives 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.
In some aspects, the composition has a weight ratio of C18:1-fatty acid derivatives to C18:2-fatty acid derivatives of greater than 1.7:1, greater than 1.8:1, greater than 1.9:1, greater than 2.0:1, greater than 2.1:1, greater than 2.2:1, greater than 2.3:1, greater than 2.4:1, or greater than 2.5:1.
In some aspects, the C16:0- and C18:0-fatty acid derivatives are present in a combined amount of 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 the composition.
In some aspects, the composition has 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 amide or ester derivatives of rosin acid of total fatty acid derivatives. Exemplary resin acids derivatives are reaction products of an amine- or hydroxyl-containing reactant with dehydroabietic acid, abietic acid, neoabietic acid, levopimaric acid, palustric acid, pimaric acid, isopimaric acid, sandaracopimaric acid (See FIG. 1 ).
In some aspects, the composition includes derivatives that are only fatty acid amides, and in other aspect, the composition includes derivatives that are only fatty acid esters. The choice of whether to include a single type of derivative, such as fatty acid amides or fatty acid esters, can be determined based on the desired properties of the final composition. For example, fatty acid esters of the disclosure, fatty acid derivatives based on a fatty acid having mixture having a weight ratio of C18:1-fatty acid derivatives to C18:2-fatty acid derivatives of less than 1.3:1, or fatty acid derivatives based on a fatty acid mixture having a total amount of C16:0 and C18:0 that is not more than 5.5% (wt) of total, can be used, optionally without mixing in any other fatty acid derivatives, in a composition to provide improved storage stability.
However, while in some instances a single source fatty acid derivative preparation is used to prepare a desired composition, in other instances different fatty acid derivative preparations are mixed to provide a composition with various desired properties, such as storage stability and one or more of beneficial dispersion, corrosion inhibition, and/or antipolymerant properties. In this regard, compositions include the fatty acid derivative can include mixtures of fatty acid derivatives formed from different fatty acid sources (e.g., from soy and canola), wherein the fatty acids from these sources have desirable fatty acid profiles (C18 partially unsaturated, etc.), can include mixtures using both fatty acid amide and fatty acid ester derivatives, or combinations thereof.
In other aspects, compositions of the disclosure can include one or more components that are different than the fatty acid derivatives of the disclosure, such as those that have similar or different beneficial properties, such as dispersant properties. For example, synthetic polymers that provide a dispersant property, can be used in conjunction with the fatty acid derivatives. Exemplary synthetic polymers that can provide a dispersant property include, but are not limited to polyesters and poly(meth)acrylates.
In yet other aspects, the composition includes derivatives that the fatty acid derivatives comprise a mixture of fatty acid amides and fatty acid esters. If a mixture of fatty acid amides and fatty acid esters these derivatives can be made from any amine group-containing reactant, and any hydroxyl group-containing reactant, such as those described herein.
In some aspects the fatty acid esters are present in the composition in an amount by weight that is greater than the fatty acid amides. For example, if the composition includes a mixture of fatty acids with the fatty acid esters in a predominant amount, the fatty acid esters can be present in an amount by weight that is 1.5 times greater, 1.75 times greater, 2.0 times greater, 2.25 times greater, 2.5 times greater, 2.75 times greater, 3.0 times greater, 3.25 times greater, or 3.5 times greater than the fatty acid amides. In some aspects the fatty acid esters and fatty acid amides are present in the composition at a weight ratio in the range of in the range of 10:1 to 1.1:1, in the range of 7.5:1 to 1.5:1, in the range of 5.5:1 to 2.0:1, in the range of 4.5:1 to 2.75:1, in the range of 4.0:1 to 3.3:1, or in the range of 3.8:1 to 3.5:1.
In some aspects, the fatty acid derivatives of the disclosure can optionally be described with regards to their material properties. For most preparations, the fatty acid derivatives can be in the form of a viscous liquid, or a semi-solid, having properties between a liquid and solid, such as a soft solid material. The choice of the starting fatty acid preparation and also the amine group- or hydroxyl group-containing reactant can affect the resulting properties of the fatty acid composition. For example, fatty acid preparations having a higher percentage of fatty acid species with higher degrees of saturation generally have a higher viscosity will correspondingly result in fatty acid derivative compositions that are highly viscous or semisolid. As an example, and with reference to the materials of the Examples, VDISTILL™ DV53 shares the same CAS number with Cestoil COLI SOFA 9500, but the VDISTILL™ DV53 is semi solid while Cestoil COLI SOFA 9500 is liquid, and these difference in properties can be attributed to less saturates (C16:0; C18:0) in Cestoil COLI SOFA 9500 is (<2.5%) and higher saturates (>13%) in VDISTILL™ DV53.
The fatty acid derivative composition can be in form of a stock or concentrate composition for addition to a process composition. The stock composition can be in neat form with essentially no, or no measurable other component (e.g., no solvent). Alternatively, the fatty acid derivatives can be present in a concentrate, such as where the fatty acid derivative is the predominant (i.e., >50% by weight) in the concentrate, with the other component(s) being a solvent or solvent mixture compatible with the fatty acid derivatives. The neat composition or concentrate can be directly added to a process composition or to process equipment, such as where the fatty acid derivatives component function as a dispersant.
In some embodiment, the disclosure provides a composition wherein the fatty acid derivatives are present in an amount greater than any other component in the composition, or in an amount greater that a total amount of all other components in the composition. For example, either the fatty acid amide, the fatty acid ester, or a mixture of the amide and ester, are present in an amount greater than any other component in the composition. In some aspects, fatty acid derivatives (the fatty acid amide, the fatty acid ester, or a mixture of the amide and ester) are present in an amount greater than about 25% (wt), greater than about 30% (wt), greater than about 35% (wt), greater than about 40% (wt), greater than about 45% (wt), greater than about 50% (wt), greater than about 55% (wt), greater than about 60% (wt), greater than about 65% (wt), or greater than about 70% (wt), in the composition. In some embodiments, the fatty acid derivatives are present in the composition in an amount in the range of about 25% (wt) to about 99% (wt), in the range of about 30% (wt) to about 98% (wt), in the range of about 35% (wt) to about 97% (wt), in the range of about 40% (wt) to about 96% (wt), in the range of about 45% (wt) to about 95% (wt), in the range of about 50% (wt) to about 95% (wt), in the range of about 55% (wt) to about 90% (wt), in the range of about 60% (wt) to about 85% (wt), in the range of about 65% (wt) to about 80% (wt), or in the range of about 70% (wt) to about 75% (wt).
In some embodiments, the fatty acid ester and the fatty acid amide are present in a weight ratio in the range of 5:95 to 95:5, respectively, or in in a weight ratio in the range of 1:10 to 10:1, or 1:5 to 5:1, respectively.
In some aspects, the disclosure provides compositions wherein the fatty acid ester is present in an amount in the range of about 20% (wt) to about 77.5% (wt), and the fatty acid amide is present in an amount in the range of about 5% (wt) to about 22% (wt), the fatty acid ester is present in an amount in the range of about 35% (wt) to about 70% (wt), and the fatty acid amide is present in an amount in the range of about 10% (wt) to about 20% (wt), or the fatty acid ester is present in an amount in the range of about 45% (wt) to about 65% (wt), and the fatty acid amide is present in an amount in the range of about 14% (wt) to about 18% (wt).
Compositions of the disclosure include fatty acid derivatives dissolved or dispersed in one or more solvents. Different solvents or solvent combinations can be used depending on the end use. For example, in some embodiments, the solvent is a water-soluble or water-miscible solvent, such as a glycol-based solvent. In other embodiments the solvent is a hydrophobic solvent such as aromatic solvents, or paraffinic solvents. Mixtures of glycol-based solvents and hydrophobic solvents can also be used.
Exemplary glycol solvents include, but are not limited, C₁-C₈glycols such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol, ethers of such glycols such as diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, and the like and combinations thereof. Commercial solvents such as Butyl Carbitol and Butyl CELLOSOLVE™, may be used and are available from Dow Chemical Company of Midland, MI.
Exemplary hydrophobic solvents include heavy aromatic naphtha, toluene, ethylbenzene, isomeric hexanes, xylene, an ethylbenzene, diesel, kerosene, and mixtures of two or more thereof.
In some embodiments, the solvent is selected from glycol, aromatic naphtha or glycol and aromatic naptha.
The concentration of one or more solvents in the antifoulant composition is not particularly limited. In some embodiments, the concentration of one or more solvents can be about 1% (wt) to about 75% (wt); about 1% (wt) to about 50% (wt); 1% (wt) to about 25% (wt); about 2.5% (wt) to about 20% (wt), about 4% (wt) to about 17.5% (wt), or about 5% (wt) to about 15% (wt).
Suitable solvents include any solvent in which a combination of the antipolymerants, antioxidants and dispersants are soluble or dispersible.
The fatty acid derivatives can be present in a composition formulated as a dispersant. In a dispersant composition, the fatty acid derivatives are able to provide the dispersant properties, and therefore other components are not necessary for dispersant activity. Accordingly, in some embodiments the disclosure provides compositions where the fatty acid derivatives are used alone or along with a solvent (e.g., a hydrocarbon solvent or glycol-based solvent as described herein), and there are either no other components in the composition, or minimal amounts of other components that are different from the fatty acid derivatives and solvents, wherein if other components are present they are in a combined amount of less than about 1% (wt), less than about 0.5% (wt), less than about 0.1% (wt), less than about 0.05% (wt), or less than about 0.01% (wt).
Optionally, the fatty acid derivative can be substituted with, or used in combination with, one or more synthetic polymer(s) that can provide a dispersant property include. Exemplary synthetic dispersant polymers include, but are not limited to, polyesters and poly(meth)acrylates, which include homopolymer and copolymers thereof. Exemplary monomers that can be used to prepare homo- or co-polymers include long chain (C16-C20)alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, and short chain (alkyl (C1-C6)alkyl (meth)acrylates. An exemplary methacrylate dispersant polymer is a polymer of butyl methacrylate, 2-(dimethylamino)ethyl methacrylate, dodecyl methacrylate and octadecyl methacrylate. See, for example, HiTec™ 5703.
In a composition, the optional synthetic dispersant polymer (e.g., polyesters and poly(meth)acrylate copolymers) can be used in an amount in the range of about 10% (wt) to about 20% (wt). If a synthetic polymer is included in an antifoulant composition including a mixture of fatty acid ester and fatty acid amide derivatives, it can replace a portion of the fatty acid derivatives, such as replacing the fatty acid amide derivatives. Accordingly, an exemplary antifoulant composition can include a fatty acid ester is present in an amount in the range of about 20% (wt) to about 77.5% (wt), and the synthetic polymer (e.g., poly(meth)acrylate copolymer) is present in an amount in the range of about 5% (wt) to about 22% (wt), the fatty acid ester is present in an amount in the range of about 35% (wt) to about 70% (wt), and the synthetic polymer is present in an amount in the range of about 10% (wt) to about 20% (wt), or the fatty acid ester is present in an amount in the range of about 45% (wt) to about 65% (wt), and the synthetic polymer is present in an amount in the range of about 14% (wt) to about 18% (wt).
A dispersant composition of the disclosure can optionally include one or more other components, as long as such components do not impair dispersant performance. For example, optionally, the dispersant composition can optionally include an antioxidant and/or antipolymerant, and accordingly the dispersant composition can also have antifoulant properties. The fatty acid derivatives can impart one or more advantageous properties to the composition, for example, increased separation of unsaturated species, leading to decreased degree of polymerization thereof; and/or increased flotation of reacted species, leading to reduced polymer deposition on equipment such as on the compressor inner surfaces.
In some embodiments, the fatty acid derivatives are present in an amount in the range of about 40 wt % to about 90 wt % in the composition, in the range of about 50 wt % to 90 wt %, about 60 wt % to about 90 wt % or about 65 wt % to 85 wt % of the composition.
In another aspect, the disclosure provides compositions and methods for improving the storage stability of a composition, such as a dispersant composition, or an antifoulant composition that includes an antioxidant and/or antipolymerant. An improvement in storage stability can be assessed by preparing a composition including fatty acid derivatives of the disclosure, storing the composition for a defined period of time under defined conditions, and then assessing the activity of the composition (e.g., with regards to dispersion properties and/or antifoulant properties) versus a comparative composition that does not have the fatty acid derivative features as described herein, under the same storage conditions.
Storage temperatures can be, for example, room temperature (about 20° C.), between room temperature and freezing (about 10° C.), at about freezing (about 0° C.), or below freezing (about −10° C.). Storage times can be, for example, about 1 week, about 1 month, about 6 months, about 1 year, or about 2 years.
In some embodiments, compositions of the disclosure include one or more antioxidant. The antioxidant can be present in an antifoulant composition with the fatty acid derivatives, and optionally one or more other compounds. Antioxidants that can be included in an antifoulant composition include those that reduce oxidative polymerization of polymerizable material in a process stream. While the antioxidants (e.g., phenol- and phenylenediamine-based) can inhibit polymerization of monomers, they are functionally different than polymerization inhibitors such as ones that are nitroxide-based, which react with monomers before they can form insoluble polymers.
Exemplary antioxidants include phenolic antioxidants, and hindered phenols, and such as phenylenediamines, thereof that are known to prevent unwanted polymerization of ethylenically unsaturated monomers by reducing oxidative polymerization.
In some embodiments, the phenolic antioxidant is a hindered or a non-hindered phenol. The phenolic antioxidant can have activity towards an ethylenically unsaturated monomer. Examples of phenolic antioxidants include hydroquinone (HQ), butylated hydroxytoluene (BHT), tert-butylcatechol (TBC), 2,6 di-tert-butyl phenol, monomethylether of hydroquinone (MEHQ), butylated hydroxyanisole, propyl gallate, butylated hydroxyanisole (BHA), tertiary butyl hydroquinone (TBHQ), tocopherol and esters thereof (e.g., tocopherol acetate), and polyphenolic antioxidants.
In some embodiments, the phenolic antioxidant is a hydroxylated quinone antioxidant such as 2,5-dihydroxy-1,4-benzoquinone, 2,5-dihydroxy-1,4-benzoquinone, 3,6-dibenzhydryl-2,5-dihydroxybenzoquinone, and 3-benzhydryl-2,5-dihydroxybenzoquinone. See for example, WO 2020/0132178 (Masere, et al.)
In some embodiments the antioxidant is a phenylenediamine. Phenylenediamines include unsubstituted phenylenediamines, N-substituted phenylenediamine, or N,N′-substituted phenylenediamine targeted towards an ethylenically unsaturated monomer, and any combination thereof. Examples of phenylenediamine are 1,4-phenylenediamine, N,N′-dimethyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N′-dibutyl-p-phenylenediamine, N-phenyl-N′-(1,4-dimethylphenyl)-p-phenylenediamine, N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine, and any combination thereof.
Phenylenediamines can also include p- or m-phenylenediamine (PDA); N,N′-diphenylphenylenediamine; N,N,N′,N′-tetramethyl-p-phenylenediamine; N,N′-bis-(1,4-dimethylpentyl)-phenylenediamine; N-phenyl-N′-(1,4-dimethylpentyl)-p-phenylenediamine; N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine; N-phenyl-N-cyclohexyl p-phenylenediamine; N,N′-dinaphthyl p-phenylenediamine; N-isopropyl-N′-phenyl p-phenylenediamine; N-aminoalkyl-N′-phenyl p-phenylenediamine; N-(2-methyl-2-aminopropyl)-N′-phenyl p-phenylenediamine; phenyl-b-isopropyl-aminophenylamine; p-hydroxydiphenylamine; p-hydroxylphenyl-b-naphthylamine; 1,8-naphthalenediamine.
Other antioxidants include oxygenated aromatic amines, such as oxygenated aminophenol-, phenyl-p-phenylenediamine-, and diaminobenzene-based compounds, including 4-bis[(2-hydroxybutyl)amino]phenol, 1,4-bis[3-butoxy-2-hydroxy-propylamino]benzene, and 1-bis[3-butoxy-2-hydroxy-propylamino]-4-phenylaminobenzene. See for example, WO 2020/223225 (Dhawan, et al.)
Hindered phenolic compounds can include o- and p-sec-butylphenol; 2,4-di-sec-butylphenol; 2,6-di-sec-butylphenol; 2,4,6-tri-sec-butylphenol; 2,4,6-trimethylphenol; butylated hydroxytoluene (BHT, also known as 2,6-tert-butyl-4-methylphenol and 2,6-tert-butyl p-cresol); 2,6-dibutyl-4-methylphenol; hydroquinone; monomethylether of hydroquinone (MEHQ); 2,6-bis (1,6 dimethylethyl-4-(1-methylpropyl) phenol), b-naphthoquinone; N-phenyl p-aminophenol; and combinations thereof.
In some embodiments, the antioxidant is 1,4-phenylenediamine, or an alkylated or phenyl derivative thereof. Exemplary alkylated or phenyl derivatives of 1,4-phenylenediamine include N,N′-di-2-butyl-1,4-phenylenediamine and N-2-butyl-N′-phenyl-1,4-phenylenediamine. Other antioxidants include ascorbic acid and esters thereof, such as ascorbyl palmitate.
In some embodiments, the antioxidant, or antioxidant mixture, is present at about 0.1% (wt) to about 25% (wt); about 0.25% (wt) to about 20% (wt); about 0.5% (wt) to about 17.5% (wt); about 0.75% (wt) to about 15% (wt); about 1% (wt) to about 12.5% (wt); about 1.25% (wt) to about 10% (wt); or about 1.5% (wt) to about 7.5% (wt) in the antifoulant composition. In some embodiments, compositions of the disclosure include one or more
antipolymerant(s). The antipolymerant can be present in an antifoulant composition with the fatty acid derivatives, and optionally one or more other compounds. Exemplary classes of antipolymerant compounds include: nitroxides (e.g., di-tert-butylnitroxide), hindered phenoxy compounds (e.g., galvinoxyl), phenothiazines, hydrazyl compounds (e.g., diphenylpicrylhydrazyl), and stabilized hydrocarbon radicals (e.g., triphenylmethyl), as well as polyradicals, and biradicals of these types. In addition, precursors that produce stable free radicals in situ can be used in the fatty acid derivative compositions and selected from the following groups: nitrones, nitrosos, thioketones, benzoquinones, and hydroxylamines.
Exemplary antipolymerants include one or more of 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO), 1-hydroxy-2,2,6,6-tetramethylpiperidine (TEMPOH), 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (HTMPO), 4-oxo-2,2,6,6-tetramethylpiperidinyl-1-oxyl (OTEMPO), 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine (HTMPOH), and 1-hydroxy-4-oxo-2,2,6,6-tetramethylpiperidine (OTEMPOH) or a combination thereof.
Other exemplary antipolymerants include 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-ethoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-propoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-butoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4 4-acetate-2,2,6,6-tetramethyl piperidinol, 4-amino-2,2,6,6-tetramethyl piperidinol, 4-acetamido-2,2,6,6-tetramethyl piperidinol, 1,2,3,6-tetrahydro-2,2,6,6-tetramethyl piperidinol, bis(2,2,6,6-tetramethylpiperidinol) sebacate, add 3,6-dihydro-2,2,6,6-tetramethyl-1 (2H)pyridinyloxy or a combination thereof.
In some embodiments, the antipolymerant is 4-hydroxy-2,2,6,6-tetramethylpiperidyl-1-oxyl. Other suitable agents to use as an antipolymerant are disclosed in U.S. Pat. No. 9,399,622, which is incorporated herein by reference in its entirety and for all purposes.
In some embodiments, the antipolymerant is present in an amount in the range of about 0.1% (wt) to about 25% (wt); about 0.25% (wt) to about 20% (wt); about 0.5% (wt) to about 17.5% (wt); about 0.75% (wt) to about 15% (wt); about 1% (wt) to about 12.5% (wt); about 1.25% (wt) to about 10% (wt); or about 1.5% (wt) to about 7.5% (wt).
In some embodiments, the composition is an antifoulant composition and includes: (a) a mixture of fatty acid derivatives, wherein the fatty acid derivatives comprise fatty acid amides, fatty acid esters, or both and wherein (i) C16:0- and C18:0-fatty acid derivatives are present in an amount of less than 15% (wt) of total fatty acid derivatives, (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), the fatty acid derivatives present in an amount in the range of about 45% (wt) to about 95% (wt), antioxidant (e.g., phenylenediamine-based) in an amount in the range of about 0.25% (wt) to about 20% (wt), antipolymerant (e.g., nitroxide-based) in an amount in the range of about 0.25% (wt) to about 20% (wt), and solvent in an amount in the range of about 1% (wt) to about 50% (wt).
In some embodiments, the composition is an antifoulant composition and includes: (a) a mixture of fatty acid derivatives, wherein the fatty acid derivatives comprise fatty acid amides, fatty acid esters, or both and wherein (i) C16:0- and C18:0-fatty acid derivatives are present in an amount of less than 15% (wt) of total fatty acid derivatives, (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), the fatty acid derivatives present in an amount in the range of about 55% (wt) to about 90% (wt), antioxidant (e.g., phenylenediamine-based) in an amount in the range of about 1% (wt) to about 12.5%, antipolymerant (e.g., nitroxide-based) in an amount in the range of about 1% (wt) to about 12.5%, and solvent in an amount in the range of about 1% (wt) to about 25% (wt).
In some embodiments, compositions of the disclosure are used in a method to prevent or reduce deposition of polymers on process equipment. For example, the compositions can be used to reduce or prevent fouling of process equipment. In other aspects, compositions of the disclosure are used to provide a dispersant function in compositions used in association with process equipment. The compositions can be used in processes for ethylene production, processing, treatment, or storage. The compositions of the disclosure can be used in processes using compressor equipment. Compositions of the disclosure can also be used to improve storage stability of a dispersant, an antioxidant, an antipolymerant, or any combination thereof.
In more specific methods the antifoulant composition is used to prevent or reduce polymer formation in process equipment such as gas compressors used in ethylene production processes.
Ethylene is typically produced industrially in a process wherein hydrocarbons are converted in a catalytic reactor or a cracking furnace. Hydrocarbon cracking is generally carried out in the presence of steam. After the hydrocarbons are cracked in the reactor, an effluent stream leads from the reactor to further processing equipment. The effluent stream which includes a variety of components including the ethylene, other hydrocarbons, and water, is cleaned and then dried to remove water. The dried and cleaned composition is then compressed and moved to an olefin recovery apparatus, in which ethylene is separated from other light hydrocarbons, such as ethane, propylene, and propane. Purification of ethylene also generally uses a distillation tower to separate ethylene from ethane in mixtures of the two compounds. Reference is made to FIG. 2 which represents an ethylene production process wherein a starting hydrocarbon composition 100, such as naphtha or liquified petroleum gas, is introduced into a steam cracking furnace 105 in the presence of steam. During cracking, saturated hydrocarbons are broken down into smaller hydrocarbons, including unsaturated hydrocarbons and saturated hydrocarbon species. After treatment for a brief period of time at high temperature, the gas is transferred from the furnace to a quencher/transfer line heat exchanger 110 using quench oil. From there, the cracked gas is moved through a series of compressors (115A-C). After compression the compressed gas is moved through a caustic tower 120 for removal of acidic gases like hydrogen sulfide and carbon dioxide, and then a dryer 125 for drying of the cracked gas. The compressed gas is then separated into carbon-specific species in a series of separation towers 125 (C3+/C4+ separation), 135 ([C2 and C3]/tail gas separation), and 145 (C2 and C3+ separation), resulting in product streams 130 (C4+), 140 (tail gas), 150 (C2), 155 (C3+), 160 (C3+), and 165 (C2 and C3) enriched for certain low molecular weight carbon species. For example, see Gholami, Z., et al. (Energies, 14, 8190, 2021). Cracked gas compressors (CGCs), which represent the most critical apparatus used in ethylene production plants, are very high-capacity centrifugal compressors with very high absorbed power ratings. In ethylene production, a “CGC train” is present as multiple bodies of multistage compressors driven by steam turbines. If a first CGC becomes fouled in a CGC train this can have a significant effect on the overall performance of the train. In an ethylene production system, the antifoulant composition of the disclosure reduces or prevents fouling of process equipment, such as fouling of charge gas compressor and affect inter-stage coolers. Fouling otherwise significantly reduces the performance of these parts of the system.
The CGC functions to compress gases from the catalytic reactor, which are then separated in downstream units within the ethylene production system. In many arrangements, a CGC train has 2-3 multistage compressors which are driven by steam turbines. Water it typically added to the process gas compressor which vaporizes in the compressor stage, absorbing some heat of compression and lowering stage discharge temperatures. The antifoulant composition of the disclosure can be added along with the water at this point into the system. The addition of water can lower processing temperatures and help control unwanted polymerization which otherwise is promoted at higher temperatures, and the presence of the antipolymerant composition of the disclosure also works minimize polymerization as well.
During ethylene production, wash oil is commonly injected at regular intervals in CGCs. Wash oil is in the form of a liquid that typically has a high concentration of aromatic hydrocarbons (typically more than 60%), boiling points of higher than 300° C., and functions to wash and reduce polymer contamination on blades of CGCs. The antipolymerant composition of the disclosure can be present in the wash oil as a way to introduce the antifoulant materials into the system. Wash oil is injected through wash oil injection nozzles which are typically mounted on suction conduit and also the return bend for each stage. The beneficial dispersant properties of the antifoulant composition of the disclosure can work in conjunction with wash oil injection to reduce the deposition of polymer foulants on internal surfaces of the CGCs. The wash oil/antifoulant mixture can dissolve and scrub polymer foulants from the metal surfaces and minimize deposition.
The CGC compresses a mixture of cracked gases that include C4, C5, and C6 hydrocarbons (higher MW). The antifoulant composition of the disclosure can prevent fouling as caused mainly by free radical polymerization, condensation, and thermal degradation to coke. In particular, the antifoulant composition of the disclosure, can prevent compounds with unsaturation such as ethylene, propylene, and butene, and as found in the gas, from reacting with heavier molecular weight (i.e., C6, C7, C8 hydrocarbon compounds) resulting in polymer formations. The antifoulant composition can therefore minimize polymer formations and fouling rates with otherwise increase with temperature. The antifoulant composition can prevent polymer chain growth which otherwise results in increase of the molecular weight of the polymer until it becomes insoluble and adheres to the metal surfaces of the CGC. In turn, the antifoulant composition of the disclosure minimizes the formation of coke-like substances otherwise formed from deposited polymer foulants, on internal parts of the compressor. Use of the antifoulant composition of the disclosure can minimize reduced capacity or unscheduled downtime of the CGC, a negatively impacts overall production and plant economics.
More generally, fouling may occur in any compressor application wherein a combination of pressure and temperature within the compressor may result in the deposition of materials on various surfaces within the compressor. Accordingly, antifoulant compositions of the disclosure can be used in processes other than ethylene production, including any process where there is a potential problem with polymer foulants forming on process apparatus surfaces. Ethylene production plants are, therefore, discussed here as an illustrative example.
The antifoulant composition can also be useful in other similar applications and with other equipment. For example, the antifoulant composition can be used with any process where process equipment will come into contact with ethylenically unsaturated monomers. For example, the composition can be used in ethylene and acrylonitrile quench water systems. The antifoulant composition can also be used with ethylene dilution steam generators and acrylonitrile purification systems. Many industrial processes have monomer recovery systems which are commonly subject to fouling and therefore are processes in which the antifoulant composition of the current disclosure can be used. Process water strippers and waste water strippers used with petrochemical processes such as styrene, butadiene, acrylonitrile, and ethylene processes are also processes and systems in which the antifoulant composition can be used. In some embodiments, ethylene acid gas scrubbers and butadiene solvent recovery systems are also applications in which antifoulant composition of the disclosure can be used. The antifoulant composition can be used in any process which has process equipment subject to polymers forming and depositing on process equipment. In addition to processes that consume or produce at least one of styrene, butadiene, acrylonitrile, and ethylene are potential applications of the antifoulant composition.
In embodiments, the antifoulant composition can prevent polymerization and deposition of the polymers on process equipment in a primary fractionation process, light ends fractionation, non-aromatic halogenated vinyl fractionation, process-gas compression, dilution steam system, caustic tower, quench water tower, butadiene extraction. In some embodiments, the antifoulant composition can prevent or reduce or delay the polymerization of resins and compositions comprising ethylenically unsaturated species.
The antifoulant composition can be added at one or more points in a process and at one or more locations. For example, the antifouling composition can be added directly at an inter-cooler or compressor, or upstream of the inter-cooler or at different stages of the same compressor.
The antifoulant composition can be added continuously or intermittently to the process equipment as required to prevent or to reduce fouling.
The antifoulant composition can be added by any suitable method. For example, the antifoulant composition can be added in the form of a concentrate, or as a dilute solution. In some embodiments, the antifoulant composition can be used as a solution, an emulsion, or a dispersion that is sprayed, dripped, poured, or injected into a desired opening within a system, or onto the process equipment or process condensate. In some embodiments, the antifoulant composition can be added with a washoil or an attemperation water.
In some embodiments, the antifoulant composition can be pumped or injected into a system in a continuous fashion or as a high-volume flush to clean the system. The injection point can be at any or all stages of the compressor train and/or to the discharge lines before each after cooler.
After the antifoulant composition is applied to process equipment it can be referred to as treated process equipment. In some embodiments, treated process equipment can be observed to undergo less polymer deposition on process equipment than on process equipment without addition of the antifoulant composition.
The effectiveness of an antifoulant composition can be assessed by the reduction or prevention of polymer formation, or reduction of polymer deposition, using any known method or test. For example, the effectiveness of an antifoulant composition can be assessed by measuring the time it takes for a simulated pygas mixture to gel. A simulated pygas mixture can contain, for example, conjugated diene (isoprene), vinyl monomer (ethenylbenzene), dimer of cyclopentadiene, and crosslinker (divinylbenzene). An exemplary simulated pygas mixture contains about 25 wt/vol % conjugated diene (isoprene), about 48 wt/vol % vinyl monomer (ethenylbenzene), about 25 wt/vol % dimer of cyclopentadiene, and about 2 wt/vol % crosslinker (divinylbenzene).
In some embodiments, using the measurements described above, polymer formation and solid deposition inside process equipment treated with the antifoulant composition is reduced by at least 50 wt % compared to process equipment not treated with the antifoulant composition. In some embodiments, about 50 wt % to 100 wt % (where 100 wt % reduction in polymer formation is elimination of deposition), or about 50 wt % to 95 wt %, or about 50 wt % to 90 wt %, or about 50 wt % to 85 wt %, or about 50 wt % to 80 wt %, or about 50 wt % to 75 wt %, or about 50 wt % to 70 wt %, or about 55 wt % to 100 wt %, or about 60 wt % to 100 wt %, or about 65 wt % to 100 wt %, or about 70 wt % to 100 wt %, or about 60 wt % to 95 wt %, or about 70 wt % to 95 wt %, or about 60 wt % to 90 wt %, or about 70 wt % to 90 wt %.
In some embodiments, fouling of treated process equipment is reduced by 50 wt % to 100 wt % compared to untreated process equipment over a 24-hour period, or 12-hour period or 1 hour period. The longer the time period of gel formation in a process equipment treated with the antifoulant composition, the less or delayed the deposition of polymers on process equipment.
While the amount of antifoulant composition used depends on a number of factors, exemplary amounts introduced into process equipment and process condensate (through either injection into the feed stream or direct injection to each compression stage) range from about 1 ppm to 500 ppm of the combination of the antifoulant composition, or about 5 ppm to 500 ppm, 10 ppm to 500 ppm, or about 20 ppm to 500 ppm, or about 30 ppm to 500 ppm, or about 40 ppm to 500 ppm, or about 50 ppm to 500 ppm, or about 60 ppm to 500 ppm, or about 70 ppm to 500 ppm, or about 80 ppm to 500 ppm, or about 90 ppm to 500 ppm, or about 100 ppm to 500 ppm, or about 5 ppm to 450 ppm, or about 5 ppm to 400 ppm, or about 5 ppm to 350 ppm, or about 5 ppm to 300 ppm, or about 5 ppm to 250 ppm, or about 5 ppm to 200 ppm, or about 5 ppm to 150 ppm, or about 5 ppm to 100 ppm, or about 10 ppm to 300 ppm, or about 10 ppm to 250 ppm, or about 50 ppm to 250 ppm, or about 50 ppm to 200 ppm based on the antifoulant compositions.

EXAMPLES

The following examples are intended to illustrate different aspect and embodiment of the invention and are not to be considered limiting the scope of the invention. It will be recognized that various modifications and changes may be made without following the experimental embodiments described herein, further without departing from the scope of the claims.
Table 2 details chemical property profiles of some commercial fatty acid preparations that are used to make fatty acid derivatives of the current disclosure.

TABLE 2

Working Examples

Commercial	Cestoil	Vantage	Industrene	PMC Biogenix
Product	COLI9500 ™	Vdistill ™ DV63	224 (PMC)	ERSFA

Veg. Source	Soy	Canola
Acid Value		196-204	200
Iodine Value		112	129
Titer (° C.)		12	14
Gardner Color		1	0.7
Wt. % C16:0	0.75	4.8	7	3.1
Wt. % C18:0	0.54	2.9	2	2.5
Wt. % C18:1	28.6	60	32	35.5
Wt. % C18:2	57.89	23.7	23	25.3
Wt. % C18:3	3.91	5.2	16	15.6
Wt. % C20:0	0	0.6	1	18
Wt. % C20:1	0		14.3
Wt. % C20:2	0		0.6
Wt. % C22:0	0
Wt. % C22:1	0		1.6
Rosin Acid	0	0
C18:1:C18:2	0.49	2.53		1.4
Total C18:1-C18:3	90.4	88.9	71	76.4
Total C16:0 +−	1.29	7.7	9	5.6
C18:0
Total C16:0 +−	1.29	7.7	10
C18:0 + C20:0 +
C22:0

Table 3 details chemical property profiles of some comparative fatty acid preparations.

TABLE 3

Comparative Examples

			Soy
			Vantage
Source	Tall	Soy	Vdistill ™ DV53

Acid Value	194	199
Iodine Value	125	132
Titer (° C.)	−4	20
Gardner Color	4.5	1.5
Wt. % C16:0	0.2	11	10-12
Wt. % C18:0	2.2	4	3-5
Wt. % C18:1	59	23	22-26
Wt. % C18:2	36	51	51-54
Wt. % C18:3	0	7	5-7
Wt. % C20:0	2-6	0.2	0-1
Wt. % C20:1
Wt. % C20:2
Wt. % C22:0
Wt. % C22:0
Rosin Acid	2-6
C18:1:C18:2	1.64	2.22	~0.46
Total C18:1-C18:3	95	81	~82.5
Total C16:0 +−	2.4	15	~15
C18:0
Total C16:0 +−		15.2	~83
C18:0 + C20:0 +
C22:0

Example 1

Synthesis of Soybean Oil Fatty Acid-Tetraethylenepentamine Derivatives (SOFA-TEPA Amide)

SOFA-TEPA amide was synthesized from a glycerol-restricted soybean oil fatty acid preparation (SOFA) from Cestoil (COLI9500™). The COLI9500™ SOFA preparation has the properties as shown in Table 1.
To a 250 mL four-necked round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stirrer bar was added glycerol-restricted soybean oil fatty acid (89.6 g) COLI9500™ obtained from Cestoil Chemical, Inc. (Courtice, Ontario, Canada). Next, tetraethylenepentamine (17.1 g, 0.090 moles) was charged to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to rise from 21° C. to about 44° C. Heavy aromatic naphtha (18.3 g) was then charged to the well-stirred reaction mixture. Nitrogen purging was started, and reaction was heated to about 170° C. and held for about 10 hours. The reaction was cooled to below 100° C., and an amount of heavy aromatic naphtha (HAN) equivalent in volume to that of the liquid collected in the Dean-Stark trap was added to the flask. The contents of the flask were stirred for a further ten minutes and allowed to cool to room temperature. The product remained a clear liquid and showed no signs of phase separation over time, as stored at room temperature and for 38 days.
A comparative SOFA-TEPA amide product was made from the soybean oil fatty acid preparation Vantage Vdistill™ DV53 (see Table 3), but the storage stability of this product was poor and it was not further tested.

Example 2

Synthesis of Soybean Oil Fatty Acid-Triethanolamine Derivatives (SOFA-TEA Ester)

SOFA-TEA ester was synthesized from Cestoil COLI9500™ SOFA. The COLI9500™ SOFA preparation has the properties as shown in Table 1.
To a 250 mL four-necked round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stirrer bar was added glycerol-restricted soybean oil fatty acid (44.97 g) COLI9500™ from Cestoil. Next, triethanolamine (15.75 g, 0.10 moles) was charged to the well-stirred reaction mixture. The reaction was heated to about 210° C. and held at that temperature for about four hours. The reaction was cooled to below 100° C., and heavy aromatic naphtha (39.28 g) was added to flask. The contents of the flask were stirred for a further ten minutes and cooled to room temperature. The product remained a clear liquid and showed no signs of phase separation, as stored at room temperature and for 1 year. Accordingly, the fatty acid esters, which are solvent based, provided surprisingly long storage stability.

Example 3

Synthesis of Canola Oil Fatty Acid-Tetraethylenepentamine Derivatives (COFA-TEPA Amide)

COFA-TEPA amide was synthesized from a glycerol-restricted canola oil fatty acid preparation (COFA) from Vantage (Vdistill™ DV63).
The Vdistill™ DV63 COFA preparation has the properties as shown in Table 1.
To a 250 mL four-necked round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stirrer bar was added glycerol-restricted canola oil fatty acid (144.4 g) Vdistill™ DV63 (Vantage, USA). Next, tetraethylenepentamine (27.4 g, 0.14 moles) was charged to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to rise from 23° C. to about 47° C. Heavy aromatic naphtha (28.3 g) was then charged to the well-stirred reaction mixture. Nitrogen purging was started, and reaction was heated to about 170° C. and held for about 12 hours. The reaction was cooled to below 100° C., and an amount of heavy aromatic naphtha (HAN) equivalent in volume to that of the liquid collected in the Dean-Stark trap was added to the flask. The contents of the flask were stirred for a further ten minutes and allowed to cool to room temperature. The product remained a clear liquid and showed no signs of phase separation over time, as stored at room temperature and for 40 days.

Example 4

Synthesis of Canola Oil Fatty Acid-Triethanolamine Derivatives (COFA-TEA Ester)

COFA-TEA ester was synthesized from Vdistill™ DV63 (Vantage).
The Vdistill™ DV63 COFA preparation has the properties as shown in Table 1.
To a 250 mL four-necked round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stirrer bar was added glycerol-restricted canola oil fatty acid (90.6 g) Vdistill™ DV63 (Vantage). Next, triethanolamine (31.5 g, 0.21 moles) was charged to the well-stirred reaction mixture. The reaction was heated to about 210° C. and held at that temperature for about four hours. The reaction was cooled to below 100° C., and heavy aromatic naphtha (78 g) was added to flask. The contents of the flask were stirred for a further ten minutes and cooled to room temperature. The product remained a clear liquid and showed no signs of phase separation over time, as stored at room temperature and for 200 days. Accordingly, the fatty acid esters, which are solvent based, provided surprisingly long storage stability.

Example 5

Storage Stability Testing of SOFA-TEPA Amide (Cestoil COLI9500™) and COFA-TEPA Amide (Vantage Vdistill™ DV63)

The SOFA-TEPA amide product from Example 1 was further diluted with xylene at 88.9 amide to 11.1 xylene ratio. The COFA-TEPA amide from Example 3 product was not diluted with xylene. The SOFA derivatives were stored for more than 1 year at room temperature. As a general matter, the fatty acid ester derivatives provided better storage stability than the corresponding fatty acids amides. The diluted version with xylene was stable, with the COFA amide stable up to 40 days at room temperature. Storage stability is measured by sample showing no solid precipitation when stored at room temperature. These compositions were then further used for creating the antifoulant products.

Examples 6 and 7

Antifoulant Compositions with Mixtures of SOFA-TEPA Amide and SOFA-TEA Ester (Cestoil COLI9500™) or COFA-TEPA Amide and COFA-TEA Ester (Vantage Vdistill™ DV63)
SOFA-TEPA amide and SOFA-TEA ester (Cestoil COLI9500™) from Examples 1 and 2, and COFA-TEPA amide and COFA-TEA ester (Vantage Vdistill™ DV63) from Examples 3 and 4 were used to make antifoulant compositions using the following components in the amounts according to Tables 3 and 4.
The antifoulant compositions were prepared by first dissolving the antipolymerant 4-hydroxy TEMPO in the solvents HAN and ethylene glycol monobutyl ether. This mixture was shaken on shaker for 20-30 minutes. Next, the amide (SOFA-TEPA or COFA-TEPA amide, respectively) and ester (SOFA-TEA ester or COFA-TEA ester, respectively) are added, followed by the phenylene diamine, and this composition was then mixed on shaker for another 15-20 minutes. All of the components were completely soluble.

	TABLE 4

	Component	Amount

	SOFA-TEPA amide (Cestoil	16% (wt)_—
	COLI ™9500-TEPA amide)
	SOFA-TEA ester (Cestoil	58% (wt)
	COLI ™9500-TEA ester)
	4-hydroxy TEMPO (antipolymerant)	2.5% (wt)
	heavy aromatic naphtha (HAN)	11% (wt)
	ethylene glycol monobutyl ether (EGMBE)	10% (wt)
	N,N-dibutyl-p-phenylenediamine (DBPD)	2.5% (wt)

	TABLE 5

	Component	Amount

	COFA-TEPA amide (Vantage	16% (wt)_—
	Vdistill ™ DV63-TEPA amide)
	COFA-TEA ester (Vantage	58% (wt)
	Vdistill ™ DV63-TEA ester)
	4-hydroxy TEMPO (antipolymerant)	2.5% (wt)
	heavy aromatic naphtha (HAN)	11% (wt)
	ethylene glycol monobutyl ether	10% (wt)
	N,N-dibutyl-p-phenylenediamine	2.5% (wt)

A comparative antifoulant composition was prepared using TEPA amine and TEA ester derivatives of tall oil fatty acid (TOFA). TOFA-TEPA amide and TOFA-TEA esters were prepared according to the process described in Vergara et al. (European Polymer Journal 97:112-119, 2017). The comparative antifoulant composition including TOFA-TEPA amide and TOFA-TEA ester, were used along with the 4-hydroxy TEMPO antipolymerant, HAN, EGMBE, and DBPD, at the same concentrations as the components in Tables 4 and 5.

Example 8

Emulsion Testing of SOFA- and COFA-Amide/Ester-Containing Antifoulant Compositions in Py-Gas Simulation Mixture

The SOFA-TEPA amide/SOFA-TEA ester-based antifoulant composition of Example 6 and the COFA-TEPA amide/COFA-TEA ester-based antifoulant composition of Example 7 were subjected to emulsion testing in a pyrolysis gas (py-gas) simulation mixture. The emulsion resolution times were measured after vigorous mixing of the antifoulant composition and the py-gas simulation mixture.
A hydrocarbon-based composition for the py-gas simulation mixture was prepared having the following components and corresponding amounts: heptane (10% wt.), dicyclopentadiene (10% wt.), cyclohexane (10% wt.), toluene (35% wt.), and styrene (35% wt.). A solution of 75% (vol.) water and 25% (vol.) of the hydrocarbon mixture was then prepared by adding 12.5 mL of the hydrocarbon mixture to 37.5 mL of water (50 mL total py-gas simulation mixture volume).
25 mL (500 ppm) of the SOFA-TEPA amide/SOFA-TEA ester-based antifoulant composition of Example 6, the COFA-TEPA amide/COFA-TEA ester-based antifoulant composition of Example 7, and the comparative TOFA-TEPA amide/TOFA-TEA ester-based antifoulant composition were individually added to the 50 mL py-gas simulation mixtures. A control composition with no antifoulant composition was also prepared and tested.
Samples were then shaken on high speed on a shaker for 1 minute and the emulsion (rag layer) resolution time was noted and are shown in Table 6.

	TABLE 6

		Emulsion
	Py-gas simulation mixture with:	Resolution Time

	No antifoulant composition	N/A
	25 mL (500 ppm) of the SOFA-TEPA	8 minutes
	amide/SOFA-TEA ester-based
	antifoulant composition
	25 mL (500 ppm) of the COFA-TEPA	8 minutes
	amide/COFA-TEA ester-based
	antifoulant composition
	25 mL (500 ppm) of the TOFA-TEPA	8 minutes
	amide/TOFA-TEA ester-based
	antifoulant composition

The emulsion resolution time in for the TOFA-based, SOFA-based, and COFA-based antifoulant compositions was about 8 minutes demonstrating the SOFA-based, and COFA-based compositions performed as well as the TOFA-based composition with regards to emulsion resolution.

Example 9

Gelation Testing of SOFA- and COFA-Amide/Ester-Containing Antifoulant Compositions in Py-Gas Simulation Mixture

The SOFA-TEPA amide/SOFA-TEA ester-based antifoulant composition of Example 6 and the COFA-TEPA amide/COFA-TEA ester-based antifoulant composition of Example 7 were subjected to gelation testing in a pyrolysis gas (py-gas) simulation mixture. The gelation times were measured to determine effects of the SOFA- and COFA-derivative products on the efficiency of the inhibitor in the antifoulant composition.
The py-gas simulation mixture of Example 8 was tested for gelation time but was found not to produce a gel in a time frame useful for determining the efficiency of an inhibitor for gelation testing. To provide a py-gas simulation mixture suitable for determining the effects of antipolymerant, the mixture was optimized by increasing the styrene amount and adjusting the components. The optimized mixture was used to determine if there was any detrimental effect on antipolymerant activity (assessing the gel time of the py-gas mixtures) when the TOFA composition was changed to a TOFA alternative (a SOFA-based or COFA-based) composition.
The optimized mixture for assessing antipolymerant activity had the following amounts of components: heptane (20.85% wt.), dicyclopentadiene (19.6% wt.), isoprene (19.6% wt.), divinylbenzene (1.96% wt.), and styrene (37.98% wt.). Isoprene and DVB were purified using the AO (inhibitor) removal kit. Styrene was purified on alumina-based column chromatography. DVB was added, followed by isoprene and styrene. Heptane was added next, and upon the heptane addition an insoluble layer was formed. DCPD solid was used as is and was dissolved in the mixture.
The simulated py-gas mixture was vigorously shaken, and then an amount of 10 mL was added to 4 different bottles. Next, 10 μL (1000 ppm) of the SOFA-TEPA amide/SOFA-TEA ester-based antifoulant composition of Example 6, the COFA-TEPA amide/COFA-TEA ester-based antifoulant composition of Example 7, and the comparative TOFA-TEPA amide/TOFA-TEA ester-based antifoulant composition were individually added to the 10 mL of each sample. The gelation reaction was performed at 130° C. using 10 mL of sample in pressure tubes.
The control (no antifoulant composition) gelled in a time of 3 hours and 50 minutes. However, all of the samples including the SOFA-, COFA-, and TOFA-based antifoulant compositions did not gel, indicating inhibitor efficiency. In this regard, the SOFA- and COFA-based antifoulant composition performed as well as the TOFA-based antifoulant composition, and no adverse effects of the SOFA- and COFA-based antifoulant composition on antipolymerant activity was seen.
Gelation experiments were conducted a second time under the same, and gel times and soluble polymer was measured and recorded.
The control sample (no antifoulant composition) was observed to thicken at 4 hours and then and gelled at 7 hours at 130° C. Under same conditions the SOFA-, COFA-, and TOFA-based antifoulant compositions did not gel and remained as free flowing liquids after 7 hrs. IPA was used to precipitate polymer in the compositions, and it was determined that the control sample (no antifoulant composition) contained significant soluble polymer besides gelled polymer. When equal amount of IPA is used to precipitate, all antifoulant solutions contain similar soluble polymer and no gelled polymer compared to blank. While all three antifoulant solutions (SOFA-, COFA-, and TOFA-based antifoulant compositions) contain similar soluble polymer the SOFA-, COFA-, and TOFA-based antifoulant compositions produced less polymer as shown in Table 7. This indicates that component(s) unique to TOFA-based antifoulant compositions could allow more soluble polymer to be formed. In particular, that lack of rosin acid in the SOFA- and COFA-based antifoulant compositions might prevent any antagonist activity of antipolymerant.

	TABLE 7

		Weight of
	Sample	soluble polymer

	Blank	1.088 g (gelled polymer
		present but could not
		be quantified)
	TOFA-TEPA amide/TOFA-TEA	1.460 g (no gel)
	ester-based antifoulant
	composition
	SOFA-TEPA amide/SOFA-TEA	1.347 g (no gel)
	ester-based antifoulant
	composition
	COFA-TEPA amide/COFA-TEA	1.311 g (no gel)
	ester-based antifoulant
	composition

Example 10

Dispersant Testing of SOFA- and COFA-Amide/Ester-Containing Antifoulant Compositions in Py-Gas Simulation Mixture

A foulant-containing system was prepared to test the ability of the SOFA-TEPA amide/SOFA-TEA ester-based antifoulant composition of Example 6, and the COFA-TEPA amide/COFA-TEA ester-based antifoulant composition of Example 7, to disperse foulant particles in a composition.
Newer foulants were obtained from a Knock out drum (D-314), and then crushed into fine powder using mortar and pestle. Particles were placed in a solution wherein larger particles were allowed to crash to the bottom and smaller particles remained suspended in solution which were selected. A solution having approximately 10 weight % small foulant particles in solution was prepared by adding 0.25 g foulant particles to 2.30 g toluene. A volume of 10 mL of hexane was placed in a test tube and 20 μL (2000 ppm) of antifoulant composition (SOFA-, COFA-, and TOFA-based antifoulant compositions) was individually added to the hexane. Next, 100-400 μL of foulant (5 drops) was introduced into each of the test tube to provide approximately the same amount of foulant for each sample, and all tubes were shaken well simultaneously. A control without antifoulant composition was also tested. After shaking, the tubes were allowed to stand and assessments were made at a zero time point, and then at 3 min, 5 min, and 7 min to observe dispersant performance.
As a general matter, the SOFA-, COFA-, and TOFA-based antifoulant compositions were able to disperse the foulant to a much greater degree thereby causing less accumulation of foulant particles in the bottom of the tube, as compared to the control sample without the fatty acid derivatives. Additionally, the tubes with the SOFA-, COFA-, and TOFA-based antifoulant compositions showed a darker color solution indicating better solubility or dispersibility of the foulant particulate, as compared to the control sample which was not as dark in color.
Accumulated foulant was measured for the control and the SOFA-, COFA-, and TOFA-based antifoulant compositions and measurement are shown in FIGS. 1 and 2 for the zero time point (immediate measurement) and the 7 minute time point. The T-4 minutes data reveals, the TOFA-based antifoulant compositions collected 75% of soluble polymer in 4 minutes while the COFA-based antifoulant compositions was <10% and SOFA-based antifoulant compositions was 50% indicating soluble polymer testing COFA>SOFA>TOFA up to 4 min.
The results demonstrate that the SOFA-, COFA-, and TOFA-based antifoulant compositions were able to significantly lower the accumulation of foulant. Surprisingly, the SOFA- and COFA-based antifoulant compositions performed better TOFA-based antifoulant composition for dispersion, with the COFA-based antifoulant composition providing the best results. See FIGS. 3 and 4 .

Example 11

Corrosion Resistance Testing of SOFA- and COFA-Amide/Ester-Containing Antifoulant Compositions

Wheel box testing (NACE 1D182, “Wheel Test Method Used for Evaluation of Film-Persistent Corrosion Inhibitors for Oil Field Applications”) was conducted to evaluate corrosion resistance of the SOFA-TEPA amide/SOFA-TEA ester-based antifoulant composition of Example 6, and the COFA-TEPA amide/COFA-TEA ester-based antifoulant composition of Example 7, relative to TOFA-based compositions. Compositions for testing were prepared with heavy aromatic naphtha, according to Table 8. A further sample of crude oil without any fatty acid derivative composition, was also evaluated.

TABLE 8

Composition A	Composition B	Composition C	Amount

TOFA-TEPA	SOFA-TEPA	COFA-TEPA	10% (wt)
amide	amide	amide
TOFA-TEA ester	SOFA-TEA ester	COFA-TEA ester	80% (wt)
Heavy aromatic	Heavy aromatic	Heavy aromatic	10% (wt)
naphtha	naphtha	naphtha

The wheel box testing was conducted with brine (49.7 NH₄Cl grams per liter and 9.9 grams per liter of HCl in water), gases were H₂S saturated, coupons were ¼″ by 7⅜″ 1018 mild steel with sandblast finish, rotation rate of the wheel was 26 revolutions per minute (RPM), test temperature 160° F. (71° C.), and the test length was 24 hours. The corrosion inhibition results are also displayed in Table 9.

TABLE 9

	Inhibitor		Std.
Sample	Concentration	% Protection	Dev.

Control	0	0.0
Composition A	5	51.0	0.5
(TOFA-based)
Composition A	10	80.0	0.0
(TOFA-based)
Composition A	20	86.0	0.0
(TOFA-based)
Composition B	5	51.0	0.0
(SOFA-based)
Composition B	10	79.5	0.5
(SOFA-based)
Composition B	20	86.0	0.0
(SOFA-based)
Composition C	5	52.5	0.5
(COFA-based)
Composition C	10	81.0	1.0
(COFA-based)
Composition C	20	86.0	1.0
(COFA-based)

These results demonstrate the corrosion resistance of SOFA-derivative and COFA-derivative compositions provided protection just as well as the TOFA-derivative formulation.

Example 12

Long Term Stability Testing of SOFA- and COFA-Amide/Ester-Containing Antifoulant Compositions

Longer term aging was conducted at room temperature and −10° C. to determine product stability.
This aging data demonstrates the stability of COFA product was similar to SOFA product in 25° C. stability and COFA and TOFA were similar at −10° C.

Claims

1. An antifoulant, antioxidant, or/and dispersant composition comprising

a mixture of fatty acid derivatives, wherein the fatty acid derivatives comprise fatty acid amides, fatty acid esters, or both and wherein

(i) C16:0- and C18:0-fatty acid derivatives are present in an amount of less than 15% (wt) of total fatty acid derivatives,

(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), and

wherein the composition has less than 2% (wt of total fatty acid derivatives) of amide or ester derivatives of resin acid and less than 5% (wt of total fatty acid derivatives) of glycerol.

2. The composition of claim 1 wherein the C18:1-, C18:2-, and C18:3-fatty acid derivatives are present in the mixture in a combined amount in the range of 60%-97.5% (wt) of total fatty acid derivatives.

3. The composition of claim 1 wherein C18:1-fatty acid derivatives are present in the mixture in an amount the range of: 25%-75% (wt) of total fatty acid derivatives.

4. The composition of claim 1, wherein the C18:2-fatty acid derivatives are present in an amount in the range of 20% (wt)-99% (wt) of total fatty acid derivatives.

5. The composition of claim 1, having a weight ratio of C18:1-fatty acid derivatives to C18:2-fatty acid derivatives of less than 1.3:1.

6. (canceled)

7. The composition of claim 1, wherein the C16:0- and C18:0-fatty acid derivatives are present in a combined amount of not more than 6% (wt) of total fatty acid derivatives.

8. An antifoulant, antioxidant, or/and dispersant composition comprising

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

9. The composition of claim 8, wherein the fatty acid derivatives comprise a mixture of the soybean oil fatty acid preparation and the canola oil fatty acid preparation.

10. The composition of claim 9, wherein:

the fatty acid esters and the fatty acid amides are present in a weight ratio in the range of 5:95 to 95:5, respectively; or

the fatty acid ester is present in an amount in the range of about 20% (wt) to about 77.5% (wt), and the fatty acid amide is present in an amount in the range of about 5% (wt) to about 22% (wt).

11. The composition of claim 8, wherein the composition has

(a) amide or ester derivatives of rosin acid in an amount of less than 1% (wt) of total fatty acid derivatives;

(b) glycerol in an amount of less than 4% (wt) of total fatty acid derivatives; or

any combination of (a) and (b).

12. (canceled)

13. The composition of claim 8 wherein

(a) the fatty acid amide comprises (ai) a hydrocarbon portion comprising 16 or more carbon groups, (aii) an amide group, and (aiii) a heteroatom portion comprising one or more heteroatoms selected from N, O, and S;

(b) the fatty acid ester comprises (bi) a hydrocarbon portion comprising 16 or more carbon groups, (bii) an ester group, and (biii) a heteroatom portion comprising one or more heteroatoms selected from N, O, and S; or

(c) both (a) and (b).

14. The composition of claim 13 wherein the heteroatom portion in the fatty acid amide or the fatty acid ester has a carbon to heteroatom ratio of 4:1 or less.

15. The composition of claim 8 wherein the fatty acid derivatives comprise a mixture of fatty acid amides and fatty acid esters.

16. The composition of claim 15 wherein the fatty acid esters are present in an amount by weight that is greater than the fatty acid amides.

17. (canceled)

18. The composition of claim 16 wherein the fatty acid esters and fatty acid amides are present at a weight ratio in the range of 7.5:1 to 1.5:1.

19. The composition of claim 8 wherein the fatty acid amide or the fatty acid ester is formed by reacting fatty acid with one or more of an amine group-containing reactant, hydroxy-group-containing reactant, or thiol group-containing reactant with a fatty acid composition comprising:

(i) C16:0- and C18:0-fatty acids present in an amount of less than 15% (wt) of total fatty acids derivatives,

(ii) C18:1-, C18:2-, and C18:3-fatty acids are present in the composition, and the amount of C18:3-fatty acids is less than 15% (wt) of total fatty acids, or

(iii) both (i) and (ii)

wherein the fatty acid composition has less than 2% (wt) of resin acids of total fatty acids and less than 0.1% (wt) of glycerol of total fatty acids.

20. (canceled)

21. The composition of claim 19 wherein:

the amine group-containing reactant is selected from linear and branched polyalkylene polyamines, aminated polyoxyalkylenes, and heterocyclic amines,

the hydroxy group containing reactant is selected from hydroxylated polyakyleneimines, polyoxyalkylenes, alcohol amines, and polyols, and

the thiol group-containing reactant comprises thiolated polyakyleneimines and thiolamines.

22.-39. (canceled)

40. A method for reducing or preventing fouling of process equipment or reducing or preventing corrosion of process equipment comprising

introducing a composition of claim 1 to the processing equipment, wherein the composition reduces or prevents fouling or corrosion of the process equipment.

41.-51. (canceled)