WO2025259738A1

WO2025259738A1 - New antifoulant for refinery applications

Info

Publication number: WO2025259738A1
Application number: PCT/US2025/033120
Authority: WO
Inventors: Omer GUL; Abuzar Syed; Ravindranath Mukkamala
Original assignee: Ecolab USA Inc
Current assignee: Ecolab USA Inc
Priority date: 2024-06-13
Filing date: 2025-06-11
Publication date: 2025-12-18
Anticipated expiration: 2026-12-13
Also published as: US20250382535A1

Abstract

Antifoulant compositions and methods of using the compositions to control fouling are provided herein. The compositions may be added to a medium, such as crude oil or a crude oil fraction. The medium may include a foulant, such as an asphaltene, and the compositions and methods provided herein are capable of dispersing the foulant, such that fouling of equipment in connection with the medium is minimized.

Description

NEW ANTIFOULANT FOR REFINERY APPLICATIONS

TECHNICAL FIELD

[0001] The present disclosure generally relates to antifoulant compositions and methods of controlling fouling using the compositions.

BACKGROUND

[0002] Asphalts and asphaltenes may be present in crude oils. These materials have been defined as dark brown to black cementitious materials in which the predominating constituents are bitumens that occur in nature or which are obtained in the processing of petroleum and crude oils. These materials characteristically contain very high molecular weight hydrocarbons, sometimes referred to as asphaltenes, and are essentially soluble in carbon disulfide, are primarily aromatic in nature, but may also be identified as containing varying amounts of sulfur, oxygen, and nitrogen.

[0003] These asphalt and asphaltene components, as well as other fouling precursors, cause varying degrees of difficulties in various processes which are aimed at recovering crude oils and preparing them for either transportation through pipelines, or in the refining, separation, or other processes required to recover valuable products from crude oil. In fact, these asphalt and asphaltene components often cause difficulty by precipitating or fouling pumps installed underground for the purpose of recovering these crude oils. Asphaltenes and other precursors are also known to foul metallic heat transfer surfaces and such fouling decreases heat transfer efficiency and clogs flow channels around or through the heat transfer equipment, heaters, and the like.

[0004] The presence of fouling precursors, including asphalts and asphaltenes, in crude oil and in other fractions of petroleum cause difficulties in the recovery, transportation, treatment and refining of these crude oils and the various fractions of crude oils in which these asphalts and asphaltenes are contained.

BRIEF SUMMARY

[0005] The present disclosure provides methods and compositions for inhibiting/controlling fouling.

[0006] In some embodiments, a method of inhibiting fouling comprises adding an effective amount of an antifouling composition to a medium, wherein the antifouling composition comprises a combination of a nonylphenol formaldehyde ethylenediamine and an ethoxylated nonylphenol, a combination of a nonylphenol formaldehyde ethylenediamine and a phosphonothioic acid ester, or a combination of an ethoxylated nonylphenol and a phosphonothioic acid ester. [0007] In some embodiments, a method of inhibiting fouling comprises adding an effective amount of an antifoulant composition to a medium, wherein the antifoulant composition comprises nonylphenol formaldehyde ethylenediamine, ethoxylated nonylphenol, and a phosphonothioic acid ester.

[0008] The present disclosure also provides antifoulant compositions. In some embodiments, an antifoulant composition of the present disclosure comprises about 1 wt. % to about 50 wt. % of a nonylphenol formaldehyde ethylenediamine, about 1 wt. % to about 40 wt. % of an ethoxylated nonylphenol, and about 1 wt. % to about 60 wt. % of a phosphonothioic acid ester.

[0009] In some embodiments, an antifoulant composition of the present disclosure comprises a combination of a nonylphenol formaldehyde ethylenediamine and an ethoxylated nonylphenol, a combination of a nonylphenol formaldehyde ethylenediamine and a phosphonothioic acid ester, or a combination of an ethoxylated nonylphenol and a phosphonothioic acid ester. [0010] The foregoing has outlined rather broadly the features and technical advantages of the present disclosure in order that the detailed description that follows may be better understood. Additional features and advantages of the disclosure will be described hereinafter that form the subject of the claims of this application.

BRIEF DESCRIPTION OF THE DRAWING

[0011] A detailed description of the invention is hereafter described with specific reference being made to the drawing in which:

[0012] FIG. 1 shows data from a Hot Liquid Process Simulator test using a three-component composition of the present disclosure and a prior art antifoulant product; and

[0013] FIG. 2 shows data from a Hot Liquid Process Simulator test using a two-component composition of the present disclosure and a three-component composition of the present disclosure.

DETAILED DESCRIPTION

[0014] Various embodiments of the present disclosure are described below. The relationship and functioning of the various elements of the embodiments may better be understood by reference to the following detailed description. However, embodiments are not strictly limited to those explicitly described below.

[0015] Examples of methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present disclosure. All publications, patent applications, patents and other reference materials mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting. [0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. [0017] Unless otherwise indicated, an alkyl group as described herein alone or as part of another group is an optionally substituted linear or branched saturated monovalent hydrocarbon substituent containing from, for example, one to about sixty carbon atoms, such as one to about thirty carbon atoms, in the main chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t- pentyl, and the like.

[0018] Compounds of the present disclosure may be substituted with suitable substituents. The term “suitable substituent,” as used herein, is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the compounds. Such suitable substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoro-alkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO-(C=O)- groups, heterocylic groups, cycloalkyl groups, amino groups, alkyl- and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylamino carbonyl groups, arylcarbonyl groups, aryloxy-carbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, suitable substituents may include halogen, an unsubstituted C1-C12 alkyl group, an unsubstituted C4-C6 aryl group, or an unsubstituted C1-C10 alkoxy group. Those skilled in the art will appreciate that many substituents can be substituted by additional substituents.

[0019] The term “substituted” as in “substituted alkyl,” means that in the group in question (e.g., the alkyl group), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups, such as hydroxy ( — OH), alkylthio, phosphino, amido ( — CON(RA)(RB), wherein RA and Re are independently hydrogen, alkyl, or aryl), amino( — N(RA)(RB), wherein RA and Re are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro ( — NO2), an ether ( — ORA wherein RA IS alkyl or aryl), an ester ( — OC(O)RA wherein RA IS alkyl or aryl), keto ( — C(O)RA wherein RA IS alkyl or aryl), heterocyclo, and the like.

[0020] When the term “substituted” introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase “optionally substituted alkyl or aryl” is to be interpreted as “optionally substituted alkyl or optionally substituted aryl.”

[0021] The present disclosure provides antifoulant compositions and methods of using the compositions to control fouling. The term “control,” as in “control” fouling, should be understood to mean, for example, reduce, inhibit, slow, prevent, minimize, etc. An illustrative, non-limiting example of controlling fouling includes dispersing and maintaining a dispersion of a foulant, such as an asphaltene, in a medium. This inhibits precipitation and formation of deposits on surfaces of equipment in contact with the medium, such as a heat exchanger and/or a crude furnace. The antifoulant compositions may be used, for example, to control fouling in a pipeline and/or a hydrocarbon refinery, or a unit thereof, such as a crude unit, a coker unit, a visbreaker unit, and any combination thereof.

[0022] The antifoulant compositions disclosed herein may be added in effective amounts to crude oil, a refinery stream, a petroleum product, or a fraction thereof, in the recovery, transportation, treatment, and/or refining of these oils and products. These compositions effectively prevent fouling of, for example, heating surfaces I heat transfer surfaces in refining operations.

[0023] In accordance with the present disclosure, an antifoulant composition may include a nonylphenol formaldehyde ethylenediamine, an ethoxylated nonylphenol, a phosphonothioic acid ester, or any combination thereof, such as a combination of a nonylphenol formaldehyde ethylenediamine and an ethoxylated nonylphenol, a combination of a nonylphenol formaldehyde ethylenediamine and a phosphonothioic acid ester, a combination of an ethoxylated nonylphenol and a phosphonothioic acid ester, or a combination of a nonylphenol formaldehyde ethylenediamine, an ethoxylated nonylphenol, and a phosphonothioic acid ester. [0024] As illustrative, non-limiting examples, the nonylphenol formaldehyde ethylenediamine may include one or more of the following molecular structures:

[0025] Each R in any of the foregoing structures is independently selected from a Ci - C20 alkyl group, such as a Ci - C18 alkyl group, a Ci - C16 alkyl group, a Ci - Cu alkyl group, a Ci - C12 alkyl group, a Ci - C10 alkyl group, a Ci

- Cs alkyl group, a Ci - Ce alkyl group, a Ci - C4 alkyl group, a Ci - C2 alkyl group, a C2 - C20 alkyl group, a C4 - C20 alkyl group, a Ce - C20 alkyl group, a Cs

- C20 alkyl group, a C10 - C20 alkyl group, a C12 - C20 alkyl group, a C14 - C20 alkyl group, C16 - C20 alkyl group, or a C18 - C20 alkyl group. [0026] Each R’ in any of the foregoing structures is independently selected from a Ci - C20 alkyl group, such as a Ci - C18 alkyl group, a Ci - C16 alkyl group, a Ci - Cu alkyl group, a Ci - C12 alkyl group, a Ci - C10 alkyl group, a Ci

- C20 alkyl group, a C10 - C20 alkyl group, a C12 - C20 alkyl group, a C14 - C20 alkyl group, C16 - C20 alkyl group, or a C18 - C20 alkyl group.

[0027] Each n in any of the foregoing structures is an integer selected from 0 to about 100, such as about 1 to about 90, about 1 to about 80, about 1 to about 70, about 1 to about 60, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 1 to about 5, about 10 to about 20, about 10 to about 30, about 10 to about 40, about 10 to about 50, about 10 to about 60, about 15 to about 25, about 0 to about 15, or about 0 to about 35.

[0028] Each m in any of the foregoing structures is an integer selected from 0 to about 100, such as such as about 1 to about 90, about 1 to about 80, about 1 to about 70, about 1 to about 60, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 1 to about 5, about 10 to about 20, about 10 to about 30, about 10 to about 40, about 10 to about 50, about 10 to about 60, about 15 to about 25, about 0 to about 15, or about 0 to about 35.

[0029] An illustrative, non-limiting example of the phosphonothioic acid ester comprises the following molecular structure: wherein R is selected from a Ci - C100 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, and wherein R1 = a Ci - C100 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups. [0030] For example, R may be selected from a Ci - C90 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, a Ci - Cso substituted or unsubstituted alkyl, alkenyl, or alkynyl group, a Ci - C70 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, a Ci - Ceo substituted or unsubstituted alkyl, alkenyl, or alkynyl group, a Ci - C50 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, a Ci - C40 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, a Ci - C30 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, a Ci - C20 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, or a Ci - C10 substituted or unsubstituted alkyl, alkenyl, or alkynyl group.

[0031] R1 may be selected from, for example, a Ci - C100 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - C90 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - Cso substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - C70 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - Ceo substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - C50 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - C40 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - C30 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a Ci - C20 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, or a Ci - C10 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, such as one, two, three, four, five, or six hydroxyl groups. [0032] In some embodiments, the Ri substituent may be selected from, for example, a Ci - C100 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group that comprises a heteroatom, such as oxygen, nitrogen, and/or sulfur as a connecting group, and having from zero to six hydroxyl groups. Some examples include Ri groups derived from tertiary amino alcohols, such as triethanolamine, N-methyl-diethanolamine, or N,N-dimethylethanolamine. Other examples include where Ri groups are derived from ether alcohols, such as diethylene glycol (HO-CH2- CH2-O- CH2- CH2-OH), and thioether alcohols, such as diethylenethioglycol (HO- CH2- CH2-S- CH2- CH2-OH).

[0033] In certain embodiments, the Ri substituent is derived from one of a mono alcohol, such as R1-OH, a diol, such as ethylene glycol, a triol, such as glycerol, or a tetraol, such as pentaerythritol.

[0034] In an illustrative embodiment, the phosphonothioic acid ester comprises the following molecular structure: wherein R is selected from a Ci - C100 substituted or unsubstituted alkyl, alkenyl, or alkynyl group as defined above.

[0035] A non-limiting example of the phosphonothioic acid ester includes polyisobutenyl phosphonothioic acid pentaerythritol ester.

[0036] An illustrative, non-limiting example of the ethoxylated nonylphenol comprises the following molecular structure: [0037] The amount of nonylphenol formaldehyde ethylenediamine in a composition of the present disclosure is not particularly limited. For example, a composition of the present disclosure may comprise from about 0 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, about 10 wt. % to about 40 wt. %, about 10 wt. % to about 35 wt. %, about 10 wt. % to about 30 wt. %, about 10 wt. % to about 25 wt. %, about 15 wt. % to about 40 wt. %, about 15 wt. % to about 35 wt. %, or about 20 wt. % to about 35 wt. % of the nonylphenol formaldehyde ethylenediamine.

[0038] The amount of ethoxylated nonylphenol in a composition of the present disclosure is not particularly limited. For example, a composition of the present disclosure may comprise from about 0 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, about 5 wt. % to about 40 wt. %, about 5 wt. % to about 30 wt. %, about 5 wt. % to about 25 wt. %, about 5 wt. % to about 20 wt. %, about 5 wt. % to about 15 wt. %, about 10 wt. % to about 25 wt. %, or about 10 wt. % to about 20 wt. % of the ethoxylated nonylphenol.

[0039] The amount of phosphonothioic acid ester in a composition of the present disclosure is not particularly limited. For example, a composition of the present disclosure may comprise from about 0 wt. % to about 60 wt. %, about 1 wt. % to about 50 wt. %, about 1 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, about 10 wt. % to about 60 wt. %, about 20 wt. % to about 60 wt. %, about 30 wt. % to about 60 wt. %, about 15 wt. % to about 45 wt. %, about 15 wt. % to about 35 wt. %, about 15 wt. % to about 25 wt. %, or about 20 wt. % to about 30 wt. % of the phosphonothioic acid ester.

[0040] In certain embodiments, a composition of the present disclosure consists of or consists essentially of the nonylphenol formaldehyde ethylenediamine, the ethoxylated nonylphenol, and/or the phosphonothioic acid ester. If a composition consists essentially of the nonylphenol formaldehyde ethylenediamine, the ethoxylated nonylphenol, and/or the phosphonothioic acid ester, it excludes other components that affect the basic and novel characteristics of the composition, such as a polycondensed aromatic/ - naphthenic compound, a compound having a thiophenic structure, a polyisobutylene derivative, and/or a dialkyl dithiophosphate metal salt.

[0041] The antifoulant compositions disclosed herein may include (or exclude) an additional additive, such as a polyisobutylene succinic anhydride, a pentaerythritol ester, a polycondensed aromatic/ -naphthenic compound, a compound having a thiophenic structure, a polyisobutylene derivative, a dialkyl dithiophosphate metal salt, and any combination thereof.

[0042] The antifoulant compositions disclosed herein may include from about 0 wt. % to about 50 wt. % of the additional additive, such as from about 1 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 25 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 15 wt. %, about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt. % of the additional additive. [0043] A composition of the present disclosure may also comprise a solvent. Illustrative, non-limiting examples of solvents include heavy aromatic naphtha, mineral oil, light aromatic naphtha, kerosene, and any combination thereof.

[0044] The amount of solvent in a composition of the present disclosure is not particularly limited. For example, a composition of the present disclosure may comprise from about 20 wt. % to about 70 wt. % of the solvent, such as from about 30 wt. % to about 70 wt. %, about 40 wt. % to about 70 wt. %, about 50 wt. % to about 70 wt. %, about 60 wt. % to about 70 wt. %, about 20 wt. % to about 60 wt. %, about 20 wt. % to about 50 wt. %, about 20 wt. % to about 40 wt. %, or about 20 wt. % to about 30 wt. %.

[0045] As will be further described below, a composition of the present disclosure may also comprise a medium. The medium may be selected from, for example, a petroleum product, crude oil, a hydrocarbon feedstock, a hydrocarbon stream, slop oil, heavy residua, atmospheric or vacuum residua, shale oil, liquified coal and tar sand effluent, or any combination thereof.

[0046] The compositions disclosed herein may be used in methods for controlling fouling of a surface of a component, such as a heat exchanger and/or a crude furnace, used in a hydrocarbon refinery, wherein the surface is exposed to a medium comprising a foulant or foulant precursor. The foulant and/or foulant precursor may include, for example, an asphaltene, a paraffin, a wax, a scale, a naphthenate, coke, or any combination thereof. The compositions may be added to the medium and/or to the surface of the component in an amount that can effectively control fouling. In some embodiments, controlling fouling includes dispersing the foulant, mitigating the foulant formation, and/or keeping the foulant dispersed in the medium so it cannot deposit on a surface in contact with the medium.

[0047] In the disclosed methods, the component of the refinery may comprise a part of a storage unit, a heat exchanger, a pipe, a pump, a flow meter, a valve, a desalter, a furnace, a coker, a distillation column, a fractionation column, an atmospheric column, a pipe still, a debutanizer, a reactor, a fluid catalytic cracking unit, a fluid catalytic cracking slurry settler, a hydrocracking unit, a steam cracking unit, a thermal cracking unit, a visbreaker, a reflux unit, a condenser, a scrubber, or any combination thereof.

[0048] For example, the component and/or surface thereof can comprise part of a heat exchanger, a crude furnace, a crude processing unit, a coker unit, a visbreaker unit, or a combination thereof.

[0049] In the methods for controlling fouling disclosed herein, the effective amount of the antifoulant composition to be added to the medium is from about 1 ppm to about 50,000 ppm, based on the total amount of fluid, such as from about 1 ppm to about 40,000 ppm, from about 1 ppm to about 30,000 ppm, from about 1 ppm to about 20,000 ppm, from about 1 ppm to about 10,000 ppm, from about 1 ppm to about 7,500 ppm, from about 1 ppm to about 5,000 ppm, from about 1 ppm to about 2,500 ppm, from about 1 ppm to about 2,000 ppm, from about 1 ppm to about 1 ,500 ppm, from about 1 ppm to about 1 ,000 ppm, from about 1 ppm to about 750 ppm, from about 1 ppm to about 500 ppm, from about 1 ppm to about 250 ppm, from about 50 ppm to about 2,000 ppm, from about 100 ppm to about 2,000 ppm, or from about 250 ppm to about 1 ,000 ppm.

[0050] A medium as disclosed herein may include, for example, a petroleum product, crude oil, a hydrocarbon feedstock, a hydrocarbon stream, slop oil, heavy residua, atmospheric or vacuum residua, shale oil, liquified coal and tar sand effluent, and the like, and any blend thereof.

[0051] The methods and compositions disclosed herein are effective for controlling fouling in a refinery component, such as heat transfer equipment, used in a hydrocarbon refinery operation, wherein a medium of the operation, which could be a hydrocarbon, for example, may be at an elevated temperature and in contact with the refinery component during operation of the refinery.

[0052] The foregoing may be better understood by reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the disclosure or its application in any way.

[0053] EXAMPLES

[0054] Performance of antifoulant compositions of the present disclosure was evaluated using Hot Liquid Process Simulator (HLPS) and compared with a prior art / commercially available antifoulant product.

[0055] As can be seen in FIG. 1 , the antifoulant composition of the present disclosure (“Candidate antifoulant”), which comprised about 35 wt. % to about 45 wt. % of nonylphenol formaldehyde ethylenediamine, about 5 wt. % to about 15 wt. % ethoxylated nonylphenol, and about 20 wt. % to about 30 wt. % polyisobutenyl phosphonothioic acid ester displayed superior performance as compared to the prior art antifoulant product, which was a functionalized high molecular weight alpha olefin co-polymer (for example, as disclosed in U.S. Patent No. 10,704,000). [0056] As can be seen in FIG. 2, another embodiment of an antifoulant composition of the present disclosure, “Candidate antifoulant-1 ”, performed similarly to Candidate antifoulant, showing that a two-component composition performs similarly to a three-component composition.

[0057] HLPS is an industry accepted test method to evaluate antifoulant chemistry performance. In this test, a desalted crude oil is used. The test conditions employed were as follows: (a) Rod Temperature: about 380 °C; Flow Rate: about 3.5 mL/min; Pressure: about 500 psi; and Reaction time: about 360 min.

[0058] In the HLPS test, a homogenized crude oil sample is passed through a heated zone at a given flow rate. During this test, the inlet, outlet, and the rod temperatures are measured and recorded. The foulant precursors are destabilized while passing through the heated zone and tend to precipitate and stick to the heated rod, resulting in reduced outlet temperature. The test is repeated with antifoulant-dosed-desalted crude. Then, the fouling curves from these tests are compared for a performance improvement.

[0059] The antifoulant composition of the present disclosure was dosed into the crude oil at about 100 ppm, as was the prior art product.

[0060] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While this invention may be embodied in many different forms, there are described in detail herein specific preferred embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. In addition, unless expressly stated to the contrary, use of the term “a” is intended to include “at least one” or “one or more.” For example, “a nonylphenol formaldehyde ethylenediamine” is intended to include “at least one nonylphenol formaldehyde ethylenediamine” or “one or more nonylphenol formaldehyde ethylenediamines”. [0061] Any ranges given either in absolute terms or in approximate terms are intended to encompass both, and any definitions used herein are intended to be clarifying and not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges (including all fractional and whole values) subsumed therein.

[0062] Any composition disclosed herein may comprise, consist of, or consist essentially of any element, component and/or ingredient disclosed herein or any combination of two or more of the elements, components or ingredients disclosed herein.

[0063] Any method disclosed herein may comprise, consist of, or consist essentially of any method step disclosed herein or any combination of two or more of the method steps disclosed herein.

[0064] The transitional phrase “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements, components, ingredients and/or method steps.

[0065] The transitional phrase “consisting of” excludes any element, component, ingredient, and/or method step not specified in the claim.

[0066] The transitional phrase “consisting essentially of” limits the scope of a claim to the specified elements, components, ingredients and/or steps, as well as those that do not materially affect the basic and novel characteristic(s) of the claimed invention.

[0067] As used herein, the term "about" refers to the cited value being within the errors arising from the standard deviation found in their respective testing measurements, and if those errors cannot be determined, then "about" may refer to, for example, within 5%, 4%, 3%, 2%, or 1 % of the cited value.

[0068] Furthermore, the invention encompasses any and all possible combinations of some or all of the various embodiments described herein. It should also be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. It is therefore intended that such changes and modifications be covered by the appended claims.

Claims

What is claimed is: 1. A method of inhibiting fouling, comprising: adding an effective amount of an antifoulant composition to a medium, wherein the antifoulant composition comprises a combination of a nonylphenol formaldehyde ethylenediamine and an ethoxylated nonylphenol, a combination of a nonylphenol formaldehyde ethylenediamine and a phosphonothioic acid ester, a combination of an ethoxylated nonylphenol and a phosphonothioic acid ester, or a combination of a nonylphenol formaldehyde ethylenediamine, an ethoxylated nonylphenol, and a phosphonothioic acid ester.

2. The method of claim 1 , wherein a molecular structure of the nonylphenol formaldehyde ethylenediamine is selected from the group consisting of:

, and any combination thereof, wherein each R is independently selected from a Ci - C20 alkyl group, wherein each R’ is independently selected from a Ci - C20 alkyl group, wherein n is an integer selected from 0 to 100, and wherein m is an integer selected from 0 to 100.

3. The method of claim 1 or claim 2, wherein the phosphonothioic acid ester comprises the following molecular structure: wherein R is selected from a Ci - C100 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, and wherein R1 is a Ci - C100 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups.

4. The method of claim 3, wherein the R1 substituent further comprises a heteroatom and/or wherein the R1 substituent is derived from a tertiary amino alcohol, an ether alcohol, or a thioether alcohol.

5. The method of claim 3, wherein the R1 substituent is derived from a mono alcohol, a diol, a triol, or a tetraol.

6. The method of any one of claims 1 to 3 or 5, wherein the phosphonothioic acid ester comprises the following molecular structure: wherein R is selected from a Ci - C100 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, optionally wherein the phosphonothioic acid ester comprises polyisobutenyl phosphonothioic acid pentaerythritol ester.

7. The method of any one of the preceding claims, wherein the ethoxylated nonylphenol comprises the following molecular structure: wherein n is an integer selected from about 1 to about 30.

8. The method of any one of the preceding claims, wherein the composition comprises from about 1 wt. % to about 50 wt. % of the nonylphenol formaldehyde ethylenediamine, from about 1 wt. % to about 40 wt. % of the ethoxylated nonylphenol, and/or from about 1 wt. % to about 60 wt. % of the phosphonothioic acid ester.

9. The method of any one of the preceding claims, wherein the effective amount is from about 1 ppm to about 50,000 ppm.

10. The method of any one of the preceding claims, wherein the composition consists of or consists essentially of the nonylphenol formaldehyde ethylenediamine and the ethoxylated nonylphenol, the nonylphenol formaldehyde ethylenediamine and the phosphonothioic acid ester, the ethoxylated nonylphenol and the phosphonothioic acid ester, or the nonylphenol formaldehyde ethylenediamine, the ethoxylated nonylphenol, and the phosphonothioic acid ester.

1 1 . The method of any one of the preceding claims, wherein the medium is selected from the group consisting of a petroleum product, crude oil, a hydrocarbon feedstock, a hydrocarbon stream, slop oil, heavy residua, atmospheric or vacuum residua, shale oil, liquified coal and tar sand effluent, and any combination thereof.

12. The method of any one of the preceding claims, wherein the method is carried out in a crude unit, a coker unit, a visbreaker unit, and any combination thereof.

13. The method of any one of the preceding claims, further comprising dispersing and/or minimizing a foulant and/or a foulant precursor in the medium.

14. A method of inhibiting fouling, comprising: adding an effective amount of an antifoulant composition to a medium, wherein the antifoulant composition comprises nonylphenol formaldehyde ethylenediamine, ethoxylated nonylphenol, and a phosphonothioic acid ester.

15. The method of claim 14, wherein a molecular structure of the nonylphenol formaldehyde ethylenediamine is selected from the group consisting of:

16. The method of claim 14 or claim 15, wherein the phosphonothioic acid ester comprises the following molecular structure: wherein R is selected from a Ci - C100 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, and wherein R1 is a Ci - C100 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, optionally wherein the phosphonothioic acid ester comprises polyisobutenyl phosphonothioic acid pentaerythritol ester.

17. The method of any one of claims 14 to 16, wherein the ethoxylated nonylphenol comprises the following molecular structure: wherein n is an integer selected from about 1 to about 30.

18. The method of any one of claims 14 to 17, wherein the composition comprises from about 1 wt. % to about 50 wt. % of the nonylphenol formaldehyde ethylenediamine, from about 1 wt. % to about 40 wt. % of the ethoxylated nonylphenol, and/or from about 1 wt. % to about 60 wt. % of the phosphonothioic acid ester.

19. The method of any one of claims 14 to 18, wherein the composition consists of or consists essentially of the nonylphenol formaldehyde ethylenediamine, the ethoxylated nonylphenol, and the phosphonothioic acid ester.

20. The method of any one of claims 14 to 19, wherein the medium is selected from the group consisting of a petroleum product, crude oil, a hydrocarbon feedstock, a hydrocarbon stream, slop oil, heavy residua, atmospheric or vacuum residua, shale oil, liquified coal and tar sand effluent, and any combination thereof.

21 . The method of any one of claims 14 to 20, wherein the method is carried out in a crude unit, a coker unit, a visbreaker unit, and any combination thereof.

22. The method of any one of claims 14 to 21 , further comprising dispersing and/or minimizing a foulant and/or a foulant precursor in the medium.

23. An antifoulant composition, comprising: about 1 wt. % to about 50 wt. % of a nonylphenol formaldehyde ethylenediamine, about 1 wt. % to about 40 wt. % of an ethoxylated nonylphenol, and about 1 wt. % to about 60 wt. % of a phosphonothioic acid ester.

24. The composition of claim 23, wherein a molecular structure of the nonylphenol formaldehyde ethylenediamine is selected from the group consisting of:

25. The composition of claim 23 or claim 24, wherein the phosphonothioic acid ester comprises the following molecular structure: wherein R is selected from a Ci - C100 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, and wherein Ri is a Ci - C100 substituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups.

26. The composition of claim 25, wherein the Ri substituent further comprises a heteroatom and/or wherein the Ri substituent is derived from a tertiary amino alcohol, an ether alcohol, or a thioether alcohol.

27. The composition of claim 25, wherein the Ri substituent is derived from a mono alcohol, a diol, a triol, or a tetraol.

28. The composition of any one of claims 23 to 25 or 27, wherein the phosphonothioic acid ester comprises the following molecular structure: wherein R is selected from a Ci - C100 substituted or unsubstituted alkyl, alkenyl, or alkynyl group, optionally wherein the phosphonothioic acid ester comprises polyisobutenyl phosphonothioic acid ester.

29. The composition of any one of claims 23 to 28, wherein the ethoxylated nonylphenol comprises the following molecular structure: wherein n is an integer selected about 1 to about 30.

30. The composition of any one of claims 23 to 29, wherein the composition consists of or consists essentially of the nonylphenol formaldehyde ethylenediamine, the ethoxylated nonylphenol, and the phosphonothioic acid ester.

31 . The composition of any one of claims 23 to 30, further comprising a petroleum product, crude oil, a hydrocarbon feedstock, a hydrocarbon stream, slop oil, heavy residua, atmospheric or vacuum residua, shale oil, liquified coal and tar sand effluent, and any combination thereof.

32. An antifoulant composition, comprising: a combination of a nonylphenol formaldehyde ethylenediamine and an ethoxylated nonylphenol, a combination of a nonylphenol formaldehyde ethylenediamine and a phosphonothioic acid ester, or a combination of an ethoxylated nonylphenol and a phosphonothioic acid ester.