New Antifoulant for Refinery Applications

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

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 C-Calkyl group, an unsubstituted C-Caryl group, or an unsubstituted C-Calkoxy group. Those skilled in the art will appreciate that many substituents can be substituted by additional substituents.

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(R)(R), wherein Rand Rare independently hydrogen, alkyl, or aryl), amino (—N (R)(R), wherein Rand Rare independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (—NO), an ether (—ORwherein Ris alkyl or aryl), an ester (—OC(O)Rwherein Ris alkyl or aryl), keto (—C(O)Rwherein Ris alkyl or aryl), heterocyclo, and the like.

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.”

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.

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/heat transfer surfaces in refining operations.

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.

As illustrative, non-limiting examples, the nonylphenol formaldehyde ethylenediamine may include one or more of the following molecular structures:

Each R in any of the foregoing structures is independently selected from a C-Calkyl group, such as a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, C-Calkyl group, or a C-Calkyl group.

Each R′ in any of the foregoing structures is independently selected from a C-Calkyl group, such as a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, a C-Calkyl group, C-Calkyl group, or a C-Calkyl group.

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.

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.

An illustrative, non-limiting example of the phosphonothioic acid ester comprises the following molecular structure:

wherein R is selected from a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, and wherein R=a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups.

For example, R may be selected from a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group, or a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group.

Rmay be selected from, for example, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, a C-Csubstituted or unsubstituted, linear or cyclic alkyl, alkenyl, or alkynyl group having from zero to six hydroxyl groups, or a C-Csubstituted 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.

In some embodiments, the Rsubstituent may be selected from, for example, a C-Csubstituted 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 Rgroups derived from tertiary amino alcohols, such as triethanolamine, N-methyl-diethanolamine, or N,N-dimethylethanolamine. Other examples include where Rgroups are derived from ether alcohols, such as diethylene glycol (HO—CH—CH—O—CH—CH—OH), and thioether alcohols, such as diethylenethioglycol (HO—CH—CH—S—CH—CH—OH).

In certain embodiments, the Rsubstituent is derived from one of a mono alcohol, such as R—OH, a diol, such as ethylene glycol, a triol, such as glycerol, or a tetraol, such as pentaerythritol.

In an illustrative embodiment, the phosphonothioic acid ester comprises the following molecular structure:

wherein R is selected from a C-Csubstituted or unsubstituted alkyl, alkenyl, or alkynyl group as defined above.

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

An illustrative, non-limiting example of the ethoxylated nonylphenol comprises the following molecular structure:

wherein n is an integer selected about 1 to about 30.

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.

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.

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.

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.

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.

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.

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.

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. %.

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.

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.