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WO2025231070A1 - Composition comprenant des dérivés d'acides gras et utilisation dans des processus industriels - Google Patents

Composition comprenant des dérivés d'acides gras et utilisation dans des processus industriels

Info

Publication number
WO2025231070A1
WO2025231070A1 PCT/US2025/026983 US2025026983W WO2025231070A1 WO 2025231070 A1 WO2025231070 A1 WO 2025231070A1 US 2025026983 W US2025026983 W US 2025026983W WO 2025231070 A1 WO2025231070 A1 WO 2025231070A1
Authority
WO
WIPO (PCT)
Prior art keywords
fatty acid
composition
less
acid derivatives
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/026983
Other languages
English (en)
Inventor
Kameswara R. Vyakaranam
Ashish Dhawan
Bassam Kamal Alnasleh
Jonathan MASERE
Ravindranath Mukkamala
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab USA Inc
Original Assignee
Ecolab USA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecolab USA Inc filed Critical Ecolab USA Inc
Publication of WO2025231070A1 publication Critical patent/WO2025231070A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/68—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/34—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/24—Emulsion properties

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • these monomer types may undesirably polymerize through radical polymerization especially at elevated temperature.
  • 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.
  • 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.
  • 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.
  • 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.
  • tall oil fatty acid derivatives 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.
  • compositions including fatty acid derivatives can include one or more antipolymerants, anti corrodents, or other compounds that provide a benefit in an industrial process.
  • 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.
  • 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).
  • 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
  • C18: l-, 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 hydroxylcontaining 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.
  • polyamines e.g., linear and branched polyalkylene polyamines, thiolated polyakyleneimines, hydroxylated polyakyleneimines
  • polyoxyalkylenes e.g., aminated polyoxyalkylenes
  • polyols e.g., alcohol amines, and thiolamines.
  • 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.
  • 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 anti oxi dant(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.).
  • anti oxi dant(s) e.g., about 0.1 % (wt) to about 25 % (wt)
  • antipolymerant(s) e.g., about 0.1 % (wt) to about 25 % (wt)
  • a polar or non-polar solvent e.g., glycol, aromatic naphtha, etc.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Figure 1 are chemical structures of various resin acids.
  • Figure 2 is a flow process diagram for an ethylene production process.
  • Figure 3 is a graph of amount of accumulated foulant in the presence of a control and various fatty acid derivative dispersant formulations.
  • Figure 4 is a graph of amount of accumulated foulant in the presence of a control and various fatty acid derivative dispersant formulations.
  • An “antifoulanf ’ 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.
  • antioxidant refers to compound(s) capable of scavenging oxygen-centered radicals through donating a hydrogen radical (H) to the oxygen-centered radicals.
  • process equipment refers to apparatus that is used in a processing method, such as the production and/or refinement of chemical compounds.
  • process equipment include compressors, fans, impellers, pumps, valves, intercoolers, 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.
  • 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.
  • 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.
  • 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 Cl 6:0- and C18:0-fatty acid derivatives, (ii) the presence of C18 partial unsaturated derivative (C18: l-, C18:2-, and C18:3-fatty acid derivatives) with C18:3-fatty acid derivatives in proportionally lower amounts, or (iii) both (i) and (ii).
  • fatty acid derivatives such as fatty acids amide and fatty acid esters
  • 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 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: l, C18:0, C18: l, C18:2, C18:3, C20:0, C20:l, and C20:2 fatty acids.
  • Acid value 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 1g of fatty acid compositions, which provides a measure of the free fatty acids in the fatty acid composition.
  • Typical acid values of fatty acid preparation are in the range of about 190-210, and fatty acid reactant composition of the used for preparation of the derivatives of the disclosure have an acid value in the range.
  • Iodine value (IV) is commonly used to define the specifications of fats and oils, and is defined by the weight amount of iodine (g) consumed by 100 grams of a fatty acid or oil due to high reactivity of iodine (a halogen) with double bonds present in the fatty acid acyl chains.
  • Iodine values reflect the degree of unsaturation in fatty acids, and the higher iodine values correlate with higher degrees of unsaturation in the fatty acid composition.
  • the titer of a fatty acid composition is the temperature (degrees Celsius), at which the composition solidifies. Fatty acid compositions with higher degrees of saturation typically have lower titers.
  • Table 1 provides a list of certain saturated and partially unsaturated fatty acid can be found in plant fatty acid preparations.
  • Palmitic acid (C16:0) and stearic acid (C18:0) are also referred to herein as “C16 and C18 saturates.”
  • C16: l fatty acids” and “C16: l fatty acid derivatives” include palmitoleic acid and sapienic acid and derivatives thereof;
  • Cl 8: 1 fatty acids” and “Cl 8: 1 fatty acid derivatives” include oleic acid, elaidic acid, vaccenic acid and derivatives thereof;
  • Cl 8:2 fatty acids” and “Cl 8:2 fatty acid derivatives” include linoleic acid and linoelaidic acid and derivatives thereof.
  • C18: l, 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.
  • 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) Cl 8: 1-, Cl 8:2-, 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 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.
  • 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 3.1% (wt), not more than 3.7%
  • saturated C16 (Cl 6:0) and Cl 8 (Cl 8:0) 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.
  • C18: l-, C18:2-, and C18:3-fatty acids are all present in the starting composition.
  • the combined amount of C18: l-, 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).
  • 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.
  • the C18: l-, 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: l-, 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.
  • Cl 8: 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.
  • partially unsaturated C18:2 fatty acids e.g., linoleic acid
  • partially unsaturated C18:2 fatty acids 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.
  • the fatty acids have a C18: l 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: l 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 Figure 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).
  • the resin acids have carboxylic acid groups and are reactive with the amine and/or hydroxy] group-containing reactants otherwise used to make the fatty acid derivatives, the presence of resin acids along with the fatty acids wall result in the formation of resin acid derivatives, which is desirably minimized or eliminated.
  • 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.
  • 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.
  • 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.
  • 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.
  • fatty acid salts produces fatty acid salts and glycerol.
  • the pH of the mixture is reduced by adding a mineral acid such as sulfuric acid, hydrochloric acid, or a combination thereof.
  • 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.
  • 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.
  • 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.
  • 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.
  • the composition has no detectable amount of fatty acid as determined from an
  • 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.
  • 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.
  • 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 Cl 8 saturates, and higher amounts of Cl 8 partial unsaturates, according to the current disclosure.
  • 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.
  • 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 Cl 8 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the starting fatty acid composition has (i) Cl 6:0- and C18:0-fatty acids present in an amount of less than 15% (wt) of total fatty acid derivatives, (ii) C18: l-, 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).
  • 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.
  • 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.
  • 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.
  • the fatty acid derivatives are any one or more of the following formulas:
  • 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.
  • 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.
  • a heteroatom portion having 8 carbon atoms with a carbon to heteroatom ratio in the range 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' - (ethylenedi oxy )bis(ethylamine), 1,1 l-diamino-3, 6, 9-tri oxaundecane, l,8-diamino-3,6- di oxaoctane, and 4, 7, 10-tri oxa- 1,13 -tridecanediamine.
  • Other amine group containing reactants include cystamine (2,2'-dithiobisethanamine).
  • heterocyclic amines include imidazoline, 2-aminoimidazole, and l(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, l-[N,N-bis(2- hydroxy ethyl)amino]-2-propanol, and N-(3-aminopropyl)di ethanolamine.
  • Other hydroxyl group containing reactants include bi s(2 -hydroxy ethyl) 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: l-, C18:2-, and C18:3-fatty acids.
  • 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.
  • 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.
  • 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.
  • a hydroxyl group-containing reactant such as an alcohol amine like TEA
  • 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.
  • a solvent such as heavy aromatic naphtha (HAN).
  • 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.
  • 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.
  • 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).
  • DETA diethylenetriiamine
  • TEPA tetraethylpentamine
  • 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.
  • the reaction product composition (i) Cl 6:0- and C18:0-fatty acid derivatives are present in an amount of less than 15% (wt) of total fatty acid derivatives, (ii) C18: l-, 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.
  • 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.
  • the C18: l-, 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.
  • the Cl 8: 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.
  • 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.
  • the composition has a weight ratio of Cl 8: 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.
  • the composition has a weight ratio of Cl 8: 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.
  • 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
  • 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 Figure 1).
  • 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.
  • fatty acid esters of the disclosure fatty acid derivatives based on a fatty acid having mixture having a weight ratio of C18: l-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.
  • wt 5.5%
  • 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 (Cl 8 partially unsaturated, etc.), can include mixtures using both fatty acid amide and fatty acid ester derivatives, or combinations thereof.
  • 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.
  • 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.
  • 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.
  • the fatty acid esters are present in the composition in an amount by weight that is greater than the fatty acid amides.
  • 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.
  • 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.
  • the fatty acid derivatives of the disclosure can optionally be described with regards to their material properties.
  • 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.
  • VDISTILLTM DV53 shares the same CAS number with Cestoil COLI SOFA 9500, but the VDISTILLTM DV53 is semi solid while Cestoil COLI SOFA 9500 is liquid, and these difference in properties can be attributed to less saturates (C 16:0; Cl 8:0) in Cestoil COLI SOFA 9500 is ( ⁇ 2.5%) and higher saturates (>13%) in VDISTILLTM 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).
  • 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.
  • 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.
  • 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.
  • fatty acid derivatives 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.
  • 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).
  • 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.
  • 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.
  • solvents or solvent combinations can be used depending on the end use.
  • the solvent is a water-soluble or water- miscible solvent, such as a glycol-based solvent.
  • 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.
  • glycol solvents include, but are not limited, Ci-Cs glycols 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 CELLOSOLVETM, 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.
  • 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.
  • the concentration of one or more solvents can be about 1 % (wt) to about 75 % (wt); about 1 % (wt) to about 50 % (wt);l % (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.
  • a dispersant composition the fatty acid derivatives are able to provide the dispersant properties, and therefore other components are not necessary for dispersant activity.
  • 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).
  • a solvent e.g., a hydrocarbon solvent or glycol- based solvent as described herein
  • 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 (Cl 6- C20)alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, and short chain (alkyl (Cl-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, HiTecTM 5703.
  • the optional synthetic dispersant polymer e.g., polyesters and poly(meth)acrylate copolymers
  • the optional synthetic dispersant polymer 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.
  • 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).
  • the synthetic polymer e.g.,poly(meth)acrylate copolymer
  • a dispersant composition of the disclosure can optionally include one or more other components, as long as such components do not impair dispersant performance.
  • 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.
  • 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.
  • 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.
  • 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.
  • the phenolic antioxidant is a hindered or a non-hindered phenol.
  • the phenolic antioxidant can have activity towards an ethylenically unsaturated monomer.
  • 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.
  • HQ hydroquinone
  • BHT butylated hydroxytoluene
  • THC tert-butylcatechol
  • MEHQ monomethylether of hydroquinone
  • BHA butylated hydroxyanisole
  • BHA butyl
  • the phenolic antioxidant is a hydroxylated quinone antioxidant such as 2,5-dihydroxy-l,4-benzoquinone, 2,5-dihydroxy-l,4-benzoquinone, 3,6- dibenzhydryl-2,5-dihydroxybenzoquinone, and 3-benzhydryl-2,5-dihydroxybenzoquinone.
  • a hydroxylated quinone antioxidant such as 2,5-dihydroxy-l,4-benzoquinone, 2,5-dihydroxy-l,4-benzoquinone, 3,6- dibenzhydryl-2,5-dihydroxybenzoquinone, and 3-benzhydryl-2,5-dihydroxybenzoquinone.
  • 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.
  • phenylenediamine examples include 1,4-phenylenediamine, N,N'- dimethyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N'-dibutyl- p-phenylenediamine, N-phenyl-N'-(l,4-dimethylphenyl)-p-phenylenediamine, N-phenyl-N'- (l,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-(l,4- dimethylpentyl)-phenylenediamine; N-phenyl-N'-( 1 ,4-dimethylpentyl)-p-phenylenediamine; N-phenyl-N'-(l,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-
  • antioxidants include oxygenated aromatic amines, such as oxygenated aminophenol-, phenyl-/?-phenylenediamine-, and diaminobenzene-based compounds, including 4-bis[(2-hydroxybutyl)amino]phenol, l,4-bis[3-butoxy-2-hydroxy- propylamino]benzene, and l-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-(l-methylpropyl) phenol), b- naphthoquinone; N-phenyl p-aminophenol; and combinations thereof.
  • BHT butylated hydroxytoluene
  • MEHQ monomethylether of hydroquinone
  • MEHQ monomethylether of hydroquinone
  • 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.
  • 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.
  • 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-/c/7-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.
  • 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-l- oxyl (TEMPO), 1 -hydroxy-2, 2, 6, 6-tetramethylpiperi dine (TEMPOH), 4-hydroxy-2,2,6,6- tetramethylpiperidinyl-l-oxyl(HTMPO),4-oxo-2,2,6,6-tetramethylpiperidinyl-l-oxyl (OTEMPO),l,4-dihydroxy -2, 2, 6, 6-tetramethylpiperi dine (HTMPOH), and 1 -hydroxy -4-oxo-
  • TEMPO 2,2,6,6-tetramethylpiperidinyl-l- oxyl
  • HTMPO 4-hydroxy-2,2,6,6- tetramethylpiperidinyl-l-oxyl
  • OTEMPO 4-oxo-2,2,6,6-tetramethylpiperidinyl-l-oxyl
  • HTMPOH 2, 6, 6-tetramethylpi
  • exemplary antipolymerants include 4-methoxy-2, 2, 6, 6-tetramethylpiperi dine- 1- oxide, 4-ethoxy-2, 2, 6, 6-tetramethylpiperi dine-1 -oxide, 4-propoxy-2, 2, 6, 6- tetramethylpiperidine-1 -oxide, 4-butoxy-2,2,6,6-tetramethylpiperidine-l-oxide, 4 4-acetate-
  • the antipolymerant is 4-hydroxy -2, 2, 6, 6-tetramethylpiperi dyl- 1-oxyl.
  • Other suitable agents to use as an antipolymerant are disclosed in US Patent No. 9,399,622, which is incorporated herein by reference in its entirety and for all purposes.
  • 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).
  • 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) Cl 8: 1-, Cl 8:2-, 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., nitro
  • 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) Cl 8: 1-, Cl 8:2-, 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-
  • antioxidant e.g
  • compositions of the disclosure are used in a method to prevent or reduce deposition of polymers on process equipment.
  • the compositions can be used to reduce or prevent fouling of process equipment.
  • 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.
  • 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.
  • Figure 2 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.
  • a starting hydrocarbon composition 100 such as naphtha or liquified petroleum gas
  • steam cracking furnace 105 During cracking, saturated hydrocarbons are broken down into smaller hydrocarbons, including unsaturated hydrocarbons and saturated hydrocarbon species.
  • the gas is transferred from the furnace to a quencher/transfer line heat exchanger 110 using quench oil.
  • 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 andC3]/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.
  • CGCs which represent the most critical apparatus used in ethylene production plants, are very high- capacity centrifugal compressors with very high absorbed power ratings.
  • a “CGC train” 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the antifoulant composition can be used with any process where process equipment will come into contact with ethylenically unsaturated monomers.
  • 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.
  • 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.
  • processes that consume or produce at least one of styrene, butadiene, acrylonitrile, and ethylene are potential applications of the antifoulant composition.
  • 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.
  • 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.
  • 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.
  • the antifoulant composition can be added in the form of a concentrate, or as a dilute solution.
  • 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.
  • the antifoulant composition can be added with a washoil or an attemperation water.
  • 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.
  • treated process equipment 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.
  • 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).
  • 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.
  • 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
  • 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.
  • exemplary amounts introduced into process equipment and process condensate range from about Ippm to 500ppm 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
  • 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 3 details chemical property profiles of some comparative fatty acid preparations.
  • SOFA-TEPA amide was synthesized from a glycerol-restricted soybean oil fatty acid preparation (SOFA) from Cestoil (COLI9500TM).
  • SOFA soybean oil fatty acid preparation
  • Cestoil Cestoil
  • the COLI9500TM SOFA preparation has the properties as shown in Table 1.
  • a comparative SOFA-TEPA amide product was made from the soybean oil fatty acid preparation Vantage VdistillTM DV53 (see Table 3), but the storage stability of this product was poor and it was not further tested.
  • [140] SOFA- TEA ester was synthesized from Cestoil COLI9500TM SOFA.
  • the COLI9500TM SOFA preparation has the properties as shown in Table 1.
  • COFA-TEPA amide was synthesized from a glycerol-restricted canola oil fatty acid preparation (COFA) from Vantage (VdistillTM DV63).
  • VdistillTM DV63 COFA preparation has the properties as shown in Table 1.
  • VdistillTM DV63 COFA preparation has the properties as shown in Table 1.
  • 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.
  • 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.
  • Antifoulant Compositions with Mixtures of SOFA-TEPA amide and SOFA-TEA ester (Cestoil COLI9500TM) or COFA-TEPA amide and COFA- TEA ester (Vantage VdistillTM DV63)
  • 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.
  • 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.
  • a hydrocarbon-based composition for the py-gas simulation mixture was prepared having the following components and corresponding amounts: heptane (10% wt.), di cyclopentadiene (10% wt.), cyclohexane (10% wt.), toluene (35% wt.), and styrene (35% wt.).
  • heptane (10% wt.)
  • di cyclopentadiene 10% wt.
  • cyclohexane 10% wt.
  • toluene 35% wt.
  • styrene 35% wt.
  • 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.
  • 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.
  • 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.
  • control sample no antifoulant composition
  • the control sample 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.
  • 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 0.25g foulant particles to 2.30 g toluene. A volume of 10 mL of hexane was placed in a test tube and 20 pL (2000 ppm) of antifoulant composition (SOFA-, COFA-, and TOFA-based antifoulant compositions) was individually added to the hexane.
  • antifoulant composition SOFA-, COFA-, and TOFA-based 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.

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Abstract

Sont divulguées des compositions comprenant des dérivés d'acides gras et des procédés utilisant les compositions en tant que dispersants, agents antisalissures ou les deux. Les compositions peuvent être utilisées pour prévenir ou réduire la formation de polymère et le dépôt de polymère dans un équipement utilisé dans des processus pétrochimiques. Les compositions dérivées d'acides gras sont préparées à partir de préparations d'acides gras, présentent de faibles quantités ou sont dépourvus d'acides résiniques et de glycérol, et présentent également de faibles quantités d'acides gras C16:0 et C18:0, et des quantités totales élevées d'acides gras C18 partiellement insaturés, et/ou les compositions dérivées d'acides gras sont préparées à partir d'acides gras de soja et/ou d'acides gras de canola. Le dérivé d'acide gras peut être utilisé dans des compositions et des procédés pour lutter contre la polymérisation indésirable, la corrosion indésirable et/ou la sédimentation indésirable de matériaux particulaires pendant des processus industriels. En outre, les compositions de la divulgation présentent l'avantage supplémentaire d'une stabilité au stockage prolongée.
PCT/US2025/026983 2024-05-01 2025-04-30 Composition comprenant des dérivés d'acides gras et utilisation dans des processus industriels Pending WO2025231070A1 (fr)

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