PARAFFIN SUPPRESSANT COMPOSITIONS AND METHODS

Abstract

Paraffin suppressant-nanoparticulate admixtures are added to petroleum oils, such as crude or refined oils, to obtain treated petroleum oils. The treated petroleum oils obtain a viscosity that is reduced by 5% to 50%, and pour point that is reduced by 0.1 C. to 5 C. compared to the same petroleum oil treated with the paraffin suppressant in the absence of the nanoparticulate, further where the comparison is made at a temperature between 60 C. and 4 C. The paraffin suppressant-nanoparticulate admixtures also obtain decreased fouling of surfaces by paraffin waxes present in many petroleum oils, when compared to the same petroleum oil treated with the paraffin suppressant in the absence of the nanoparticulate.

Claims

1. A paraffin suppressant composition comprising a mixture of: a paraffin suppressant and 0.010 wt % to 1.000 wt % of a nanoparticulate based on the weight of the paraffin suppressant, wherein the paraffin suppressant is one or more paraffin inhibitors, one or more paraffin dispersants, one or more pour point depressants, or any combination of two or more thereof.

2. The paraffin suppressant composition of claim 1 wherein the nanoparticulate comprises carbon, silica, alumina, aluminosilicate, or any combination thereof.

3. The paraffin suppressant composition of claim 1 wherein the nanoparticulate comprises a Halloysite nanotube, an activated carbon, a carbon nanotube, a graphene quantum dot, Buckminsterfullerene, a colloidal silica, an agglomerated silica, or a fumed silica.

4. The paraffin suppressant composition of claim 1 further comprising a solvent, the solvent comprising one or more C1-C12 alkanols, one or more linear, branched, or cyclic C5 to C16 alkanes, benzene, toluene, o-xylene, m-xylene, p-xylene, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol mono-methyl ether acetate, N,N-dimethyl acetamide, light aromatic naphtha, heavy aromatic naphtha, fuel oil, kerosene, diesel, or any combination thereof, further wherein the solvent is present at 10 wt % to 99 wt % of the paraffin suppressant composition.

5. The paraffin suppressant composition of claim 1 wherein the paraffin suppressant comprises one or more ethylene-vinyl acetate copolymers, one or more alkoxylated alkylphenol resins, one or more acrylate ester copolymers, one or more maleimide copolymers, or any combination thereof.

6. The paraffin suppressant composition of claim 1 wherein the paraffin suppressant comprises one or more ethoxylated nonylphenols, one or more nonylphenol formaldehyde resins, dodecyl benzene sulfonic acid or a conjugate base thereof, or any combination thereof.

7. A method of forming a paraffin suppressant composition, the method comprising dispersing a paraffin suppressant in a first solvent to form a paraffin suppressant dispersion; and mixing a nanoparticulate with the paraffin suppressant dispersion to form a paraffin suppressant composition, wherein the paraffin suppressant is one or more paraffin inhibitors, one or more paraffin dispersants, one or more pour point depressants, or any combination of two or more thereof.

8. The method of claim 7 wherein the first solvent comprises one or more C1-C12 alkanols, one or more linear, branched, or cyclic C5 to C16 alkanes, benzene, toluene, o-xylene, m-xylene, p-xylene, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol mono-methyl ether acetate, N,N-dimethyl acetamide, light aromatic naphtha, heavy aromatic naphtha, fuel oil, kerosene, diesel, or any combination thereof.

9. The method of claim 7 wherein the nanoparticulate comprises carbon, silica, alumina, aluminosilicate, or any combination thereof.

10. The method of claim 7 wherein the mixing is mixing the paraffin suppressant dispersion with a dry nanoparticulate.

11. The method of claim 7 wherein the mixing is mixing the paraffin suppressant dispersion with a nanoparticulate dispersion, the nanoparticulate dispersion comprising a second solvent selected from methanol, ethanol, isopropanol, xylene, methyl ethyl ketone, ethylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol mono-methyl ether acetate, N,N-dimethyl acetamide, or any mixture thereof.

12. The method of claim 7 wherein the mixing comprises sonicating.

13. A treated petroleum oil comprising a. a petroleum oil; and b. 0.01 ppm to 10,000 ppm by weight of a paraffin suppressant composition, the paraffin suppressant composition comprising: i. a paraffin suppressant comprising one or more paraffin inhibitors, one or more paraffin dispersants, one or more pour point depressants, or any combination of two or more thereof; and ii. 0.01 wt % to 1.000 wt % of a nanoparticulate based on the weight of the paraffin suppressant.

14. The treated petroleum oil of claim 13 wherein the viscosity of the treated petroleum oil measured at a temperature between 60 C. and 4 C. is 5% to 50% less than the viscosity of a composition measured at the same temperature and comprising the crude oil and the paraffin inhibitor in the absence of the nanoparticulate.

15. The treated petroleum oil of claim 13 wherein the nanoparticulate comprises silica, alumina, an aluminosilicate, carbon, or any combination thereof.

16. The treated petroleum oil of claim 13 wherein the one or more paraffin dispersants comprise an ethoxylated long-chain phenol, a nonylphenol formaldehyde resin, dodecyl benzene sulfonic acid or a conjugate base thereof, or any combination thereof.

17. The treated petroleum oil of claim 16 wherein the petroleum oil is a crude oil, optionally wherein the crude oil is a high paraffin crude oil.

18. A method of treating a petroleum oil, the method comprising mixing 0.01 ppm to 10,000 ppm by weight of a paraffin suppressant composition of claim 1 with a petroleum oil.

19. The method of claim 18, wherein the method further comprises dispersing the paraffin suppressant in a first solvent to form a paraffin suppressant dispersion; and admixing the nanoparticulate with the paraffin suppressant dispersion to form the paraffin suppressant composition, wherein the first solvent comprises one or more C1-C12 alkanols, one or more linear, branched, or cyclic C5 to C16 alkanes, benzene, toluene, o-xylene, m-xylene, p-xylene, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol mono-methyl ether acetate, N,N-dimethyl acetamide, light aromatic naphtha, heavy aromatic naphtha, fuel oil, kerosene, diesel, or any combination thereof.

20. The method of claim 19 wherein the nanoparticulate dispersion comprises the nanoparticulate and a second solvent selected from methanol, ethanol, isopropanol, xylene, methyl ethyl ketone, ethylene glycol, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol mono-methyl ether acetate, N,N-dimethyl acetamide, or any mixture thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIG. 1 is a plot showing viscosity as a function of temperature for a light crude oil treated with a paraffin suppressant composition in accordance with Example 2.

[0020] FIG. 2 is another plot showing viscosity as a function of temperature for a light crude oil treated with a paraffin suppressant composition in accordance with Example 2.

[0021] FIG. 3 is a plot showing viscosity as a function of temperature for a heavy crude oil treated with a paraffin suppressant composition in accordance with Example 2.

[0022] FIG. 4 is another plot showing viscosity as a function of temperature for a heavy crude oil treated with a paraffin suppressant composition in accordance with Example 2.

[0023] FIG. 5 is a bar chart showing the percent decrease in viscosity for a crude oil treated using 250 ppm, 500 ppm, and 1000 ppm of a paraffin suppressant composition, in accordance with Example 4.

DETAILED DESCRIPTION

[0024] Although the present disclosure provides references to preferred embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. Various embodiments will be described in detail with reference to the drawings, wherein like reference numerals represent like parts and assemblies throughout the several views. Reference to various embodiments does not limit the scope of the claims attached hereto. Additionally, any examples set forth in this specification are not intended to be limiting and merely set forth some of the many possible embodiments for the appended claims.

Definitions

[0025] 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. Preferred 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 invention. All publications, patent applications, patents and other references 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.

[0026] The terms comprise(s), include(s), having, has, can, contain(s), and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms a, and and the include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments comprising, consisting of and consisting essentially of, the embodiments or elements presented herein, whether explicitly set forth or not.

[0027] As used herein, the term optional or optionally means that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances in which it does not.

[0028] As used herein, the term about modifying, for example, the quantity of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity that can occur, for example, through typical measuring and handling procedures used for making compounds, compositions, concentrates or use formulations; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods, and like proximate considerations. The term about also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture. Where modified by the term about the claims appended hereto include equivalents to these quantities. Further, where about is employed to describe a range of values, for example about 1 to 5 the recitation means 1 to 5 and about 1 to about 5 and 1 to about 5 and about 1 to 5 unless specifically limited by context.

[0029] As used herein, the word substantially modifying, for example, the type or quantity of an ingredient in a composition, a property, a measurable quantity, a method, a position, a value, or a range, employed in describing the embodiments of the disclosure, refers to a variation that does not affect the overall recited composition, property, quantity, method, position, value, or range thereof in a manner that negates an intended composition, property, quantity, method, position, value, or range. Examples of intended properties include, solely by way of nonlimiting examples thereof, flexibility, partition coefficient, rate, solubility, temperature, and the like; intended values include thickness, yield, weight, concentration, and the like. The effect on methods that are modified by substantially include the effects caused by variations in type or amount of materials used in a process, variability in machine settings, the effects of ambient conditions on a process, and the like wherein the manner or degree of the effect does not negate one or more intended properties or results; and like proximate considerations. Where modified by the term substantially the claims appended hereto include equivalents to these types and amounts of materials.

[0030] As used herein, the term solvent means a single compound or a mixture of two or more compounds, wherein the compound or mixture thereof is substantially liquid within at least a portion of the range between 0 C. and 100 C. at 1 atm.

[0031] As used herein, the terms solution and dispersion each indicate an isotropic mixture of a solvent with one or more compounds (solutes), wherein the one or more compounds are either dissolved therein, or homogeneously dispersed therein, or is/are capable of becoming dissolved or homogeneously dispersed therein.

[0032] As used herein, the term non-aqueous means excluding or substantially excluding water, where substantially excluding water means that a composition or material has about 5 wt % water or less, or about 4 wt % water or less, or about 3 wt % water or less, or about 2 wt % water or less, or about 1 wt % water or less, or about 0.1 wt % water or less, or about 0.01 wt % water or less.

[0033] As used herein, the term dry refers to a solid material that includes 5 wt % or less of any liquid entrained, absorbed, and/or adsorbed therein and/or thereon. In some cases, as determined by context, dry refers to a solid material that includes 5 wt % or less of water entrained, absorbed, and/or adsorbed therein and/or thereon.

[0034] As used herein, the term monomer is used in context to mean either an unsaturated compound or the polymerized residue thereof (that is, a repeat unit).

[0035] As used herein, the term copolymer means a polymer derived from more than one species of monomer. The term therefore includes polymers comprising the residues of two different monomers as well as terpolymers comprising the residues of three different monomers, tetrapolymers comprising the residues of four different monomers, and higher copolymers.

[0036] As used herein, the term crude oil means the unrefined hydrocarbon product of a subterranean reservoir, wherein the product includes a plurality of linear and/or branched alkanes having the general formula C.sub.nH.sub.2n+2, wherein n is about 5-60, and least one of the one or more of the linear and/or branched alkanes is a liquid at about 20 C. and at a pressure of about 1 atmosphere.

[0037] As used herein, the term petroleum oil refers to a crude oil obtained from a subterranean reservoir or a refined (processed) oil derived therefrom, and including one or more hydrocarbons having the general formula C.sub.nH.sub.2n+2 that are liquid at 20 C./1 atm.

[0038] As used herein, the terms paraffin and paraffin wax refer to hydrocarbons derived from or present in a petroleum oil and having the general formula C.sub.nH.sub.2n+2 wherein n is 18 or greater. In some embodiments, n is 18-200, or 18-150, or 18-100, or 18-60.

[0039] As used herein, the term high paraffin or high paraffin wax as applied to a petroleum oil means that the petroleum oil includes 3 wt % or more paraffin.

[0040] As used herein, the term paraffin suppressant means one or more paraffin inhibitors, one or more paraffin dispersants, one or more pour point depressants, or a mixture of two or more thereof.

[0041] As used herein, the term paraffin inhibitor means a polymeric compound, an oligomeric compound, or a mixture thereof, that retards, delays, minimizes, reduces, inhibits, prevents, or disrupts the crystallization or precipitation of paraffin in a petroleum oil to which it is added.

[0042] As used herein, the term paraffin dispersant means an oligomeric compound, a non-polymeric compound such as a surfactant, or any mixture thereof that disperses, dissolves, or otherwise entrains a paraffin wax in a petroleum oil to which it is added.

[0043] As used herein, the term pour point depressant means any compound that decreases the pour point of a petroleum oil to which it is added.

[0044] As used herein, the term pour point means the lowest temperature at which a petroleum oil will obtain gravity-induced flow, as determined by preheating a sample of the oil at 60 C. for 1 hour, then cooling while tilting the sample 90 at a series of predefined temperature intervals; further wherein the pour point of the oil is defined to be the temperature at which the sample obtains no observable flow for 5 seconds after initiating the tilt.

First Embodiments

[0045] Disclosed in first embodiments herein are paraffin suppressant compositions. The paraffin suppressant compositions of first embodiments comprise, consist essentially of, or consist of an admixture of one or more nanoparticulates with one or more paraffin suppressants. In any one more first embodiments herein, a paraffin suppressant comprises, consists essentially of, or consists of one or more paraffin inhibitors, one or more pour point depressants, one or more paraffin dispersants, or any mixture of two or more thereof.

[0046] In any one more paraffin suppressant compositions of first embodiments, suitable paraffin inhibitors include copolymers of ethylene with one or more of: vinyl acetate, acrylonitrile, or one or more -olefins. Such ethylene copolymers, suitably formed using conventional polymerization methodology, often include at least 10 mole % ethylene content and up to 90 mole % ethylene content, depending on the comonomer(s) incorporated, for example 10 mole % to 15 mole %, 15 mole % to 20 mole %, 20 mole % to 25 mole %, 25 mole % to 30 mole %, 30 mole % to 35 mole %, 35 mole % to 40 mole %, 40 mole % to 45 mole %, 45 mole % to 50 mole %, 50 mole % to 55 mole %, 55 mole % to 60 mole %, 60 mole % to 65 mole %, 65 mole % to 70 mole %, 70 mole % to 75 mole %, 75 mole % to 80 mole %, 80 mole % to 85 mole %, or 85 mole % to 90 mole % ethylene.

[0047] In some first embodiments herein, an ethylene-vinyl acetate copolymer includes a mole ratio of ethylene to vinyl acetate that is between 10:1 and 1:10, such as 10:1 to 9:1, 9:1 to 8:1, 8:1 to 7:1, 7:1 to 6:1, 6:1 to 5:1, 5:1 to 4:1, 4:1 to 3:1, 3:1 to 2:1, 2:1 to 1:1, 1:1 to 2:3, 1:1 to 3:4, 1:1 to 4:5, 1:1 to 5:6, 4:5 to 2:3, 4:5 to 3:4, 5:6 to 2:3, 5:6 to 3:4, 5:6 to 4:5, 1:1 to 3:5, 1:1 to 1:2, 1:2 to 1:3, 1:3 to 1:4, 1:4 to 1:5, 1:5 to 1:6, 1:6 to 1:7, 1:7 to 1:8, 1:8 to 1:9, 1:9 to 1:10, about 1:1, about 1:2, about 2:3, about 3:4, about 3:5, about 4:5, or about 5:6. In some first embodiments herein, an ethylene-acrylonitrile copolymer includes and mole ratio of ethylene to acrylonitrile between 10:1 and 1:10, such as 10:1 to 9:1, 9:1 to 8:1, 8:1 to 7:1, 7:1 to 6:1, 6:1 to 5:1, 5:1 to 4:1, 4:1 to 3:1, 3:1 to 2:1, 2:1 to 1:1, 1:1 to 1:2, 1:2 to 1:3, 1:3 to 1:4, 1:4 to 1:5, 1:5 to 1:6, 1:6 to 1:7, 1:7 to 1:8, 1:8 to 1:9, 1:9 to 1:10, about 1:1, about 1:2, about 2:3, about 3:4, about 4:5, or about 3:5.

[0048] As used in any one or more embodiments herein, the term -olefin refers to an olefin (alkene) compound, or a repeat unit formed therefrom and present in a polymer or copolymer thereof, as determined by context. An -olefin monomer has the general formula C.sub.nH.sub.2n where n is an integer between 3 and 30, such as between 3 and 26, or between 3 and 24, or between 3 and 22, or between 3 and 20, or between 3 and 18, or between 3 and 16, such as 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30; or any mixture of such compounds having a linear or branched configuration; and wherein the -olefin compound is distinguished by having one double bond in the primary or alpha () position of the alpha-olefin molecule, i.e. the sole double bond in the molecule is between the first and second carbon atoms.

[0049] Many -olefins are available as mixtures of compounds with a distribution of lengths of the alkyl side chains. For example, a C10-C14 -olefin in some embodiments is a mixture of alpha-olefins of various lengths of alkyl side chain, the C10-C14 -olefin having a number average distribution of chain lengths, wherein the distribution has a single number-maximum that lies at from C10 to C14. Therefore the term an -olefin herein also refers to a mixture of -olefins differing from each other in length of alkyl side chain, the mixture comprising a distribution of chain lengths, the distribution having a single maximum. The plural term -olefins refers to a mixture of -olefins differing from each other in length of alkyl side and/or degree of branching of the alkyl side chain, the mixture comprises a distribution of chain lengths with two or more maxima.

[0050] In some such embodiments, an ethylene-olefin copolymer includes a mole ratio of ethylene to the total of the one or more -olefin repeat units that is between 10:1 and 1:10, such as 10:1 to 9:1, 9:1 to 8:1, 8:1 to 7:1, 7:1 to 6:1, 6:1 to 5:1, 5:1 to 4:1, 4:1 to 3:1, 3:1 to 2:1, 2:1 to 1:1, 1:1 to 1:2, 1:2 to 1:3, 1:3 to 1:4, 1:4 to 1:5, 1:5 to 1:6, 1:6 to 1:7, 1:7 to 1:8, 1:8 to 1:9, or 1:9 to 1:10.

[0051] Further in any one more paraffin suppressant compositions of first embodiments, suitable paraffin inhibitor polymers include alkaryl condensation copolymers, such as alkylphenol-formaldehyde copolymers. Such copolymers are the condensation products of an alkylphenol with formaldehyde, in some embodiments further including phenol or resorcinol as up to 20 wt % of the overall copolymer content. In any one or more such first embodiments, an alkylphenol monomer is a substituted phenol having formula I,

##STR00001##

wherein the substituent R.sup.1 is a hydrocarbyl group selected from C1-C60 alkyl and C1-C60 alkaryl, and is often C6-C18 alkyl. In some embodiments, R.sup.1 is or includes C9 (nonyl). In some embodiments, R.sub.1 is attached to the para position of the alkylphenol. When subjected to conventional condensation conditions in the presence of formaldehyde, the alkylphenol, optionally further including phenol, resorcinol, or another substituted phenolic compound, forms a heavily branched paraffin inhibitor polymer.

[0052] Further in any one more paraffin suppressant compositions of first embodiments, suitable paraffin inhibitor polymers include N-functionalized polyethyleneimines, which are polymers having a structure [CH.sub.2CH.sub.2NR.sup.2].sub.m[CH.sub.2CH.sub.2NH].sub.n wherein m is an integer between 1 and 100, n is 0 or an integer between 1 and 100, and where n is an integer, the ratio of m repeat units to n repeat units is 1:1 or greater; and R.sup.2 is a C1-C60 linear or branched hydrocarbyl group, such as a C1, C2, C3, C2-C4, C3-C5, C4-C6, C5-C7, C7-C9, C8-C10, C10-C14, C11-C13, C12-C14, C13-C15, C14-C16, C15-C17, C16-C18, C17-C19, C18-C20, C20-C22, C22-C24, C24-C26, C26-C28, C28-C30, C30-C40, C40-C50, or C50-C60; further wherein R.sup.2 is the same or different for each m repeat unit. In some such embodiments, the N-functionalized polyethyleneimine is linear; in other embodiments, the N-functionalized polyethyleneimine is branched.

[0053] Further in any one more paraffin suppressant compositions of first embodiments herein, suitable paraffin inhibitor polymers include acrylate comb polymers having alkyl side chains, including alkylacrylamide, acrylate ester, and methacrylate ester homo- and copolymers; and OMAC copolymers, which are olefin-maleate ester and olefin-maleimide copolymers.

[0054] Acrylate comb polymers are synthesized using conventional additional polymerization methodology and comprise, consist essentially of, or consist of homopolymers and copolymers of monomers having the formula II,

##STR00002##

wherein R.sup.3, R.sup.4, and R.sup.5 are individually selected from hydrogen and methyl; and X is selected from NHR.sup.6 and OR.sup.6, wherein R.sup.6 is a C5-C60 linear or branched hydrocarbyl group, such as a C5-C7, C7-C9, C8-C10, C10-C14, C11-C13, C12-C14, C13-C15, C14-C16, C15-C17, C16-C18, C17-C19, C18-C20, C20-C22, C22-C24, C24-C26, C26-C28, C28-C30, C30-C40, C40-C50, C50-C60 hydrocarbyl group that is a linear or branched alkyl, alkenyl, alkaryl, or aralkyl group. In embodiments, two or more monomers having formula II are copolymerized to form the comb polymer. In some embodiments, one or more monomers having formula II are further copolymerized with a minor amount, such as 30 mole % or less, of acrylic acid or a conjugate base thereof, methacrylic acid or a conjugate base thereof, itaconic acid or a conjugate base thereof, maleic acid or a conjugate base thereof, acrylamide, methacrylamide, or a mixture of two or more thereof. In some embodiments, one or more monomers having formula II are further copolymerized with ethylene or an olefin, such as an -olefin, including any one or more of the C3-C50 -olefins described above.

[0055] Some non-limiting examples of suitable acrylate comb polymers are described in patent publications WO 2003/014170; WO 2006/075109; WO 2014/095408; EP 0 359 061; DE 38 07 394; and DE 38 07 395. Blends of acrylate comb polymers with ethylene-vinyl ester polymers are described in WO 2014/095412.

[0056] Further in any one more first embodiments herein, suitable paraffin inhibitor polymers include OMAC comb copolymers, which are copolymers of one or more olefins, such as ethylene or any one or more of the -olefins described above, with a maleimide in accordance with formula III,

##STR00003##

wherein R.sup.7 and R.sup.8 are individually selected from hydrogen and C1-C50 alkyl and R.sup.9 is a C5 to C60 hydrocarbyl group, such as a C5-C7, C7-C9, C8-C10, C10-C14, C11-C13, C12-C14, C13-C15, C14-C16, C15-C17, C16-C18, C17-C19, C18-C20, C20-C22, C22-C24, C24-C26, C26-C28, C28-C30, C30-C40, C40-C50, C50-C60 hydrocarbyl group that is a linear or branched alkyl, alkenyl, alkaryl, or aralkyl group. In embodiments, at least one of R.sup.7 and R.sup.8 is hydrogen. In embodiments, both R.sup.7 and R.sup.8 are hydrogen. In some embodiments, the OMAC comb copolymer includes the polymerized residue of one or more amide monomers in accordance with formula IIIa,

##STR00004##

wherein R.sup.7, R.sup.8, and R.sup.9 are the same as in formula III; and X is NHR.sup.8, N(R.sup.8).sub.2, OR.sup.8, or OH or a conjugate base thereof.

[0057] In some embodiments, an OMAC comb copolymer includes more than one -olefin copolymerized therewith. In some such embodiments, the OMAC comb copolymer includes the polymerized residues of two or more of: a C12-C16 -olefin; a C17-C19 -olefin; a C22-C32 -olefin; and a C32-C52 -olefin, further as described in U.S. Pat. No. 10,738,138.

[0058] In any one or more paraffin suppressant compositions herein, suitable paraffin inhibitor polymers, including any of the foregoing paraffin inhibitor polymers have a weight average molecular weight expressed as g/mol, or Da, of about 1,000 to about 5,000,000, in embodiments about 1,000 to about 4,000,000, in embodiments about 1,000 to about 3,000,000, in embodiments about 1,000 to about 2,000,000, in embodiments about 1,000 to about 1,000,000, in embodiments about 1,000 to about 500,000, in embodiments about 1,000 to about 100,000, in embodiments about 1,000 to about 50,000, in embodiments about 1,000 to about 40,000, in embodiments about 1,000 to about 35,000, in embodiments about 1,000 to about 30,000, in embodiments about 1,000 to about 25,000, in embodiments about 1,000 to about 20,000, in embodiments about 1,000 to about 15,000, in embodiments about 1,000 to about 10,000, in embodiments about 1,000 to about 7,000, in embodiments about 1,000 to about 5,000, in embodiments about 1,000 to about 3,000, in embodiments about 1,000 to about 2,000, in embodiments about 3,000 to about 5,000, in embodiments about 5,000 to about 10,000, in embodiments about 10,000 to about 30,000, in embodiments about 30,000 to about 50,000, in embodiments about 50,000 to about 100,000, in embodiments about 100,000 to about 200,000, in embodiments about 200,000 to about 500,000, in embodiments about 500,000 to about 1,000,000, in embodiments about 1,000,000 to about 2,000,000, in embodiments about 2,000,000 to about 3,000,000, in embodiments about 3,000,000 to about 4,000,000, and in embodiments about 4,000,000 to about 5,000,000.

[0059] The paraffin inhibitors listed above are effective for preventing, retarding, delaying, minimizing, reducing, and/or inhibiting paraffin precipitation, solidification, or deposition from crude oil and/or are effective for redispersing paraffin after such processes. Examples of the effect of paraffin inhibitors include preventing the precipitation of paraffin, reducing the precipitation of paraffin, or redispersing paraffin into crude oil or crude oil compositions.

[0060] As used herein, the term paraffin suppressant composition means a composition comprising, consisting of, or consisting essentially of an admixture of one or more paraffin suppressants and one or more nanoparticulates.

[0061] In any one more paraffin suppressant compositions of first embodiments, suitable paraffin dispersants include ammonium dodecyl benzene sulfonic acid (DDBSA) and alkoxylated alcohols. In some such embodiments, suitable alkoxylated alcohols include ethoxylated C5 to C60 alkanols, propoxylated C5 to C60 alkanols, and ethoxylated/propoxylated C5 to C60 alkanols comprising a random, block, or alternating copolymer of ethylene oxide and propylene oxide.

[0062] In any one more paraffin suppressant compositions of first embodiments, suitable paraffin dispersants are selected from alkoxylated alcohols having formula IV,

##STR00005##

wherein R.sup.10 is hydrogen or C1-C6 alkyl group, R.sup.11 is a linear or branched C5-C50 hydrocarbyl group, such as a C5-C7, C7-C9, C8-C10, C10-C14, C11-C13, C12-C14, C13-C15, C14-C16, C15-C17, C16-C18, C17-C19, C18-C20, C20-C22, C22-C24, C24-C26, C26-C28, C28-C30, C30-C40, C40-C50, C50-C60 hydrocarbyl group that is a linear or branched alkyl, alkenyl, alkaryl, or aralkyl group; and p and q are individually 0 or an integer from 1 to 100, with the proviso that the sum of p+q is 1 to 200, such as 1 to 3, 3 to 5, 5 to 7, 7 to 9, 9 to 11, 11 to 13, 13 to 15, 15 to 20, 20 to 25, 25 to 30, 30 to 35, 35 to 40, 40 to 45, 45 to 50, 50 to 60 60 to 70, 70 to 80, 80 to 90, 90 to 100, 100 to 110, 110 to 120, 120 to 130, 130 to 140, 140 to 150, 150 to 160, 160 to 170, 170 to 180, 180 to 190, or 190 to 200; and p and q further describe a random, blocky, or alternating arrangement of ethoxy repeat units p and propoxy repeat units q.

[0063] In any one more paraffin suppressant compositions of first embodiments, suitable paraffin dispersants are prepared by known techniques, for example reacting an alkanol with ethylene oxide, propylene oxide, or ethylene oxide and propylene oxide in the presence of a base catalyst selected from the hydroxides of alkaline or alkali earth metals or from mixed oxides of magnesium-zinc, magnesium-tin, magnesium-titanium or magnesium-antimony, or acids like sulfuric acid, or Lewis acids like titanium tetrachloride. Random copolymers can be prepared by known techniques, e.g. by the simultaneous combination of ethylene oxide and propylene oxide with catalyst. Similarly, block copolymers can be prepared by known techniques including sequential addition of different alkene oxides to the reaction mixture comprising a catalyst. Non-limiting examples of some alkoxylated alcohol polymers useful as the paraffin dispersant are commercially available for example from KLK Oleo of Selangor, Malaysia under the brand name SERDOX. The synthesis and/or use of similar and/or such alkoxylated alcohol polymers is described, for example, in U.S. Pat. Nos. 5,750,796; 7,335,235; and 8,524,643.

[0064] In any one more paraffin suppressant compositions of first embodiments, one or more paraffin dispersants are usefully admixed with one or more paraffin inhibitors to more effectively address the paraffin present in a particular crude oil, such as a crude oil having a high paraffin content and/or a high-melting paraffin fraction. In some such embodiments, the ratio of the one or more paraffin inhibitors to the one or more paraffin dispersants present in a paraffin suppressant composition of first embodiments herein is usefully between 100:1 and 1:100, depending on the type(s) of paraffin dispersants and paraffin inhibitors employed and the type of crude oil being addressed, for example 50:1 to 1:100, or 100:1 to 1:50, or 40:1 to 1:100, or 100:1 to 1:40, or 30:1 to 1:100, or 100:1 to 1:30, or 20:1 to 1:100, or 100:1 to 1:20, or 10:1 to 1:100, or 100:1 to 1:10, or 5:1 to 1:100, or 100:1 to 1:5, or 1:1 to 1:100, or 100:1 to 1:1, or 50:1 to 1:50, or 40:1 to 1:40, or 30:1 to 1:30, or 20:1 to 1:20, or 10:1 to 1:10, or 5:1 to 1:5, or 2:1 to 1:2, or 10:1 to 1:1, or 1:1 to 1:10, or 5:1 to 1:1, or 1:1 to 1:5, or 2:1 to 1:1, or 1:1 to 1:2, or about 100:1, or about 50:1, or about 40:1, or about 30:1, or about 20:1, or about 10:1, or about 5:1, or about 4:1, or about 3:1, or about 2:1, or about 1:1, or about 1:2, or about 1:3, or about 1:4, or about 1:5, or about 1:10, or about 1:20, or about 1:30, or about 1:40, or about 1:50, or about 1:100.

[0065] In any one more paraffin suppressant compositions of first embodiments, suitable pour point depressants include any of paraffin inhibitors listed above. In some embodiments a pour point depressant and a paraffin inhibitor share the same chemical composition, and the molecular weight of the paraffin inhibitor is greater than the molecular weight of the pour point depressant. In some such embodiments, the molecular weight of the paraffin inhibitor is at least an order of magnitude greater than the molecular weight of the pour point depressant.

[0066] In any one more paraffin suppressant compositions of first embodiments, suitable pour point depressants further include carboxy and siloxy esters. Carboxy fatty esters have the formula R.sup.12COOR.sup.13 wherein R.sup.12 is a C10-C50 alkaryl, aralkyl, alkyl, or alkenyl group, and R.sup.13 is the residue of a C1-C10 alkanol having 1, 2, 3, 4, 5, or 6 hydroxyl (OH) groups. One useful example of a carboxy ester pour point depressant is pentaerythritol tetrastearate. Siloxy esters have the formula (R.sup.14).sub.rSi(OR.sup.15).sub.4-r; wherein r is 1, 2, or 3, and R.sup.14 and R.sup.15 are independently selected from C5-C50 alkaryl, aralkyl, alkyl, or alkenyl groups. One useful example of a siloxy ester pour point depressant is phenyltristearyloxysilane.

[0067] In any one more paraffin suppressant compositions of first embodiments, one or more pour point depressants are usefully present in an admixture with one or more paraffin inhibitors in order to more effectively address the pour point of a particular petroleum oil, such as a crude oil having a high paraffin content, a refined oil having a high-melting fraction, or a refined or crude oil otherwise having a pour point that is about the same as, or is higher than, one or more use temperatures, where use temperatures mean the temperatures experienced by a petroleum oil as it is moved, stored, transported, poured, or pumped. In some such embodiments, the weight ratio of the one or more paraffin inhibitors to the one or more pour point depressants present in a paraffin suppressant composition of first embodiments herein is usefully between 100:1 and 1:100, depending on the type(s) of paraffin dispersants and paraffin inhibitors employed and the type of crude oil being addressed, for example 50:1 to 1:100, or 100:1 to 1:50, or 40:1 to 1:100, or 100:1 to 1:40, or 30:1 to 1:100, or 100:1 to 1:30, or 20:1 to 1:100, or 100:1 to 1:20, or 10:1 to 1:100, or 100:1 to 1:10, or 5:1 to 1:100, or 100:1 to 1:5, or 1:1 to 1:100, or 100:1 to 1:1, or 50:1 to 1:50, or 40:1 to 1:40, or 30:1 to 1:30, or 20:1 to 1:20, or 10:1 to 1:10, or 5:1 to 1:5, or 2:1 to 1:2, or 10:1 to 1:1, or 1:1 to 1:10, or 5:1 to 1:1, or 1:1 to 1:5, or 2:1 to 1:1, or 1:1 to 1:2, or about 100:1, or about 50:1, or about 40:1, or about 30:1, or about 20:1, or about 10:1, or about 5:1, or about 4:1, or about 3:1, or about 2:1, or about 1:1, or about 1:2, or about 1:3, or about 1:4, or about 1:5, or about 1:10, or about 1:20, or about 1:30, or about 1:40, or about 1:50, or about 1:100 by weight of the one or more paraffin inhibitors to the one or more pour point depressants present in a paraffin suppressant composition of first embodiments herein.

[0068] In any one or more paraffin suppressant compositions of first embodiments, the one or more nanoparticulates comprise, consist essentially of, or consist of alumina, silica, carbon, or a combination thereof. In any one more paraffin suppressant compositions of first embodiments herein, a nanoparticulate comprises, consists essentially of, or consists of a discrete group of particles having an average particle size between 1 nm and 1000 nm as determined by a volume-based method such as light scattering. In some paraffin suppressant compositions of first embodiments herein, the nanoparticulate comprises, consists essentially of, or consists of two or more discrete groups of different nanoparticles, or nanoparticle species, wherein the two or more nanoparticle species differ by chemical composition, particle size, polydispersity of particle size distribution, arrangement of layers (where at least one of the nanoparticle species has a layered structure), or two or more of these. Accordingly, references herein to the nanoparticulate or a nanoparticulate refers to a either a species of nanoparticulate that is present alone (that is, as the sole nanoparticulate species) in a paraffin suppressant composition; or to an admixture of any two or more nanoparticulate species in a paraffin suppressant composition, as determined by context.

[0069] In any of first embodiments herein, a nanoparticulate useful in one or more paraffin suppressant compositions comprises, consists essentially of, or consists of silica, alumina, zirconia, titania, magnesium oxide, iron oxide, manganese oxide, copper oxide, nickel oxide, carbon, or any combination of these. In embodiments, a nanoparticulate consists essentially of or consists of alumina. In embodiments, a nanoparticulate consists essentially of or consists of silica. In embodiments, a nanoparticulate consists essentially of or consists of an aluminosilicate. In embodiments, an aluminosilicate nanoparticulate is a layered alumina-silica nanoparticulate. In embodiments, an aluminosilicate nanoparticulate is a clay. In embodiments, a silica nanoparticulate comprises, consists essentially of, or consists of a colloidal silica or a fumed silica. In embodiments, a nanoparticulate comprises, consists essentially of, or consists of graphene, graphite, graphene oxide, or reduced graphene oxide. In embodiments, a nanoparticulate comprises, consists essentially of, or consists of activated carbon, carbon nanotubes, graphene quantum dots, Buckminsterfullerene, or any combination thereof.

[0070] In embodiments, a nanoparticulate is suitably characterized as one or more of: mesoporous, annular, spherical, planar, aggregated, or layered. In embodiments, the nanoparticulate is characterized as having a surface area of about 20 m.sup.2/g to about 1500 m.sup.2/g, such as 100 m.sup.2/g to 1500 m.sup.2/g, or 200 m.sup.2/g to 1500 m.sup.2/g, or 300 m.sup.2/g to 1500 m.sup.2/g, or 400 m.sup.2/g to 1500 m.sup.2/g, or 500 m.sup.2/g to 1500 m.sup.2/g, or 600 m.sup.2/g to 1500 m.sup.2/g, or 700 m.sup.2/g to 1500 m.sup.2/g, or 800 m.sup.2/g to 1500 m.sup.2/g, or 900 m.sup.2/g to 1500 m.sup.2/g, or 1000 m.sup.2/g to 1500 m.sup.2/g, or 1100 m.sup.2/g to 1500 m.sup.2/g, or 1200 m.sup.2/g to 1500 m.sup.2/g, or 1300 m.sup.2/g to 1500 m.sup.2/g, or 1400 m.sup.2/g to 1500 m.sup.2/g, or 20 m.sup.2/g to 1200 m.sup.2/g, or 20 m.sup.2/g to 1000 m.sup.2/g, or 20 m.sup.2/g to 900 m.sup.2/g, or 20 m.sup.2/g to 800 m.sup.2/g, or 20 m.sup.2/g to 700 m.sup.2/g, or 20 m.sup.2/g to 600 m.sup.2/g, or 20 m.sup.2/g to 500 m.sup.2/g, or 20 m.sup.2/g to 400 m.sup.2/g, or 20 m.sup.2/g to 300 m.sup.2/g, or 20 m.sup.2/g to 200 m.sup.2/g, or 20 m.sup.2/g to 100 m.sup.2/g, or m.sup.2/g to 50 m.sup.2/g, or 50 m.sup.2/g to 100 m.sup.2/g, or 100 m.sup.2/g to 200 m.sup.2/g, or 200 m.sup.2/g to 300 m.sup.2/g, or 300 m.sup.2/g to 400 m.sup.2/g, or 400 m.sup.2/g to 500 m.sup.2/g, or 500 m.sup.2/g to 600 m.sup.2/g, or 600 m.sup.2/g to 700 m.sup.2/g, or 700 m.sup.2/g to 800 m.sup.2/g, or 800 m.sup.2/g to 900 m.sup.2/g, or 900 m.sup.2/g to 1000 m.sup.2/g, or 1000 m.sup.2/g to 1100 m.sup.2/g, or 1100 m.sup.2/g to 1200 m.sup.2/g, or 1200 m.sup.2/g to 1300 m.sup.2/g, or 1300 m.sup.2/g to 1400 m.sup.2/g, or 1400 m.sup.2/g to 1500 m.sup.2/g.

[0071] In any one more paraffin suppressant compositions of first embodiments herein, a nanoparticulate is characterized as having a mean particle size or an average particle size in the range of about 1 nm to about 1000 nm when measured using a volume-dependent method of measurement, such as light scattering. For example, in various embodiments, a nanoparticulate is characterized as having a mean particle size or an average particle size of 1 nm to 1000 nm, 1 nm-900 nm, or 1 nm-800 nm, or 1 nm-700 nm, or 1 nm-600 nm, or 1 nm-500 nm, or 1 nm-400 nm, or 1 nm-300 nm, or 1 nm-200 nm, or 1 nm-100 nm, or 1 nm-50 nm, or 1 nm-10 nm, or 10 nm-1000 nm, or 20 nm-1000 nm, or 100 nm-1000 nm, or 200 nm-1000 nm, or 300 nm-1000 nm, or 400 nm-1000 nm, or 500 nm-1000 nm, or 600 nm-1000 nm, or 700 nm-1000 nm, or 800 nm-1000 nm, or 900 nm-1000 nm, or 1 nm-5 nm, or 5 nm-10 nm, or 10 nm-15 nm, or 15 nm-20 nm, or 20 nm-30 nm, or 30 nm-40 nm, or 40 nm-50 nm, or 50 nm-60 nm, or 60 nm-70 nm, or 70 nm-80 nm, or 80 nm-90 nm, or 90 nm-100 nm, or 100 nm-110 nm, or 110 nm-120 nm, or 120 nm-130 nm, or 130 nm-140 nm, or 140 nm-150 nm, or 150 nm-160 nm, or 160 nm-170 nm, or 170 nm-180 nm, or 180 nm-190 nm, or 190 nm-200 nm, or 100 nm-200 nm, or 1 nm to 200 nm, or 5 nm to 200 nm, or 100 nm-150 nm, or 150 nm-200 nm, or 200 nm-250 nm, or 250 nm-300 nm, or 1 nm to 300 nm, or 5 nm to 300 nm, or 300 nm-350 nm, or 350 nm-400 nm, or 400 nm-450 nm, or 450 nm-500 nm, or 500 nm-600 nm, or 600 nm-700 nm, or 700 nm-800 nm, or 800 nm-900 nm when measured using light scattering.

[0072] In any one more paraffin suppressant compositions of first embodiments herein, the nanoparticulate comprises, consists essentially of, or consists of silica. In embodiments the silica is a colloidal silica or a fumed silica. Colloidal silica is available as a stabilized aqueous or non-aqueous dispersion of amorphous silicon dioxide particles. Colloidal silica is conventionally synthesized by polymerization of silicates in water and under alkaline conditions, resulting in formation of a stable aqueous dispersion of highly uniform, highly spherical nanoscale colloidal particles having particle sizes ranging between 1 nm and 1000 nm, often between 5 nm and 500 nm, or even between 5 nm and 200 nm. Fumed silica is an amorphous, powdered (substantially dry) particulate synthesized by pyrolysis of silicon tetrachloride. Fumed silica particles have the same molecular composition as colloidal silica particles, but they are substantially dry and provided in powdered form instead of a stabilized liquid dispersion. Further, fumed silica primary particles are further fused as three-dimensional secondary particles; and the secondary particles may further be agglomerated as tertiary particles, whereas colloidal silica consists of or consists essentially of primary particles. The primary particle size of fumed silica is about 5 nm to 50 nm, providing a surface area of 50 m.sup.2/g-600 m.sup.2/g.

[0073] Aqueous silica nanoparticle dispersions are available commercially having between 1 wt % and about 50 wt % silica solids, often between 5 wt % and 40 wt % silica solids, present as colloidal silica nanoparticles ranging in size between 1 nm and 1000 nm, between 5 nm and 500 nm, or between 5 nm and 200 nm. Non-aqueous silica nanoparticle dispersions are also available synthetically or commercially. Commercially, silica nanoparticle dispersions are available in non-aqueous solvents, including methanol, ethanol, isopropanol, xylene, methyl ethyl ketone, ethylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol mono-methyl ether acetate, N,N-dimethyl acetamide, or mixtures thereof from the Nissan Chemical America Corporation of Houston, TX. Such non-aqueous colloidal dispersions, or organosols, include between 10 wt % and 40 wt % colloidal silica particles; and often have a colloid particle size ranging between 9 nm and 100 nm.

[0074] In any one more paraffin suppressant compositions of first embodiments herein, the nanoparticulate comprises, consists essentially of, or consists of alumina. Alumina colloids (stabilized aqueous or nonaqueous dispersions of alumina particles) are available commercially from several sources wherein an average particle size is about 200 nm or less, for example 1 nm-200 nm, or 1 nm-150 nm, or 1 nm-100 nm, or 1 nm-50 nm, or 1 nm-20 nm, or 1 nm-10 nm, or 10 nm-20 nm, or 20 nm-50 nm, or 50 nm-100 nm, or 100 nm-150 nm, or 150 nm-200 nm. In any one more paraffin suppressant compositions of first embodiments herein, a nanoparticulate comprises, consists essentially of, or consists of alumina-coated silica. Alumina-coated silica colloids are commercially available from CD Bioparticles of Shirley, NY; or under the trade name LEVASIL from Nouryon of Houston, TX. Alternatively, alumina-coated silica colloids may be synthesized, for example by using the techniques set forth in Jin et al., Colloids and Surfaces A: Physicochemical and Engineering Aspects Volume 441, pp. 170-177 (2014) or Chen et al., Ceramics International Volume 46, Issue 1, pp. 196-203 (2020).

[0075] In any one more paraffin suppressant compositions of first embodiments herein, a nanoparticulate comprises, consists essentially of, or consists of a nanoclay. Nanoclays are layered mineral silicates (phyllosilicates) that vary according to the chemical composition and morphology. Suitable nanoclay particulates include talc (Mg.sub.3[Si.sub.4O.sub.10(OH).sub.2]), vermiculite (similar to talc but including additional layers of water molecules), mica (KAl.sub.2[AlSi.sub.3O.sub.10(OH).sub.2]), kaolin (Al.sub.2[Si.sub.2O.sub.5(OH).sub.4]), montmorillonite (Mg.sub.0.33Al.sub.1.67 [Si.sub.4O.sub.10(OH).sub.2](Ca, Na).sub.x (H.sub.2O).sub.n), serpentine (Mg.sub.3[Si.sub.2O.sub.5(OH).sub.4]) and sepiolite (Mg.sub.4[Si.sub.6O.sub.15](OH).sub.2 4H.sub.2O) as well as more complex structures such as chlorite. Clay nanoparticulates, or nanoclays, may be obtained from a mined ore as a raw mineral product. Since they are naturally sourced, clay particulates, including nanoclays, can have variable and/or irregular dimensions.

[0076] One example of a useful nanoclay is halloysite, (Al.sub.2Si.sub.2O.sub.5(OH).sub.4.Math.2H.sub.2O), a layered nanotube that is chemically similar to kaolin and having CAS No. 1332-58-7. A nanotube is a discrete particulate structure having a hollow cylindrical morphology with a cylinder outer diameter of 1 micron or less and a ratio of length to outer diameter of 10 to 10,000. The nanotube structure includes an outer surface defining an outer diameter, and an inner surface defining an inner diameter, the inner and outer surfaces defining a length having distal ends, the inner surface further defining a channel or lumen extending between the distal ends thereof.

[0077] Since they are natural materials, halloysite particle dimensions are variable. In embodiments, the length of a halloysite nanotube cylinder ranges from 10 nanometers (nm) to 10 microns (m), most often about 100 nm to about 2 m, while the inner surface diameter (that is, the lumen diameter) is 5 nm to 150 nm, often about 15 nm, and the outer surface diameter is dictated by the number of layers, wherein one layer is reported by various sources to be 7 thick. Generally, the nanotubes are bilayered or have a multiple bilayer structure. Bilayer structures are formed by neighboring alumina and silica layers, further wherein associated waters of hydration cause a natural curving or curling to result in a characteristic cylindrical morphology having different chemistries on the inner and outer surfaces thereof.

[0078] In any one more paraffin suppressant compositions of first embodiments herein, a nanoparticulate comprises, consists essentially of, or consists of carbon. In embodiments, a carbon nanoparticulate comprises, consists essentially of, or consists of graphene, graphite, graphene oxide, or reduced graphene oxide. In embodiments, a nanoparticulate comprises, consists essentially of, or consists of activated carbon, carbon nanotubes, graphene quantum dots, Buckminsterfullerene, or a combination of two or more of these.

[0079] Activated carbon particulates are well known to those of skill in the art and are commercially available in a wide range of average particle sizes and porosities. In some embodiments, an activated carbon is derived from one or more of coconut shell, orange peel, bamboo fiber, rice husk, sewage sludge, or bone. In embodiments, an activated carbon particulate has a surface area of at least 500 m.sup.2/g, often 1000 m.sup.2/g or greater, or 2000 m.sup.2/g or greater, or even 3000 m.sup.2/g or greater. In embodiments, an activated carbon particulate is macroporous, nanoporous, microporous, or mesoporous. In embodiments, an activated carbon particulate is a mixture of two or more activated carbon particulates differing in one or more properties related to surface area, pore size, or average particle size.

[0080] Graphene quantum dots (GQD) are graphene fragments having a particle size that is small enough to cause exciton confinement and a quantum size effect. Typically, GQD have diameters of about 1 nm to about 20 nm, such as about 1 nm, about 2 nm, 3 about nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 11 nm, about 12 nm, about 13 nm, about 14 nm, about 15 nm, about 16 nm, about 17 nm, about 18 nm, about 19 nm, or about 20 nm. Depending on the method of preparation, one or more functional groups may be bonded to the GQD at the edge(s) thereof, wherein any one such functional group comprises or consists of one or more hydroxyl, carbonyl, carboxyl, amino, amido, mercapto, or hydrocarbyl groups.

[0081] Carbon nanotubes are singly-layered graphene sheets in cylindrical form, typically having a cylinder height ranging from about 1 nm to several microns, and inner diameters of about 0.5 nm to about 2.0 nm, such as about 0.5 nm, about 0.6 nm, about 0.7 nm, about 0.8 nm, about 0.9 nm, about 1.0 nm, about 1.1 nm, about 1.2 nm, about 1.3 nm, about 1.4 nm, about 1.5 nm, about 1.6 nm, about 1.7 nm, about 1.8 nm, about 1.9 nm, or about 2.0 nm. Depending on the method of preparation, one or more functional groups may be bonded to a carbon nanotube at one or both ends of the cylinder, wherein any one such functional group comprises or consists of one or more hydroxyl, carbonyl, carboxyl, amino, amido, mercapto, or hydrocarbyl groups. Multi-walled carbon nanotubes are annularly nested single-wall carbon nanotubes. Double- and triple-walled carbon nanotubes are known.

[0082] Buckminsterfullerene is a spherical molecule made up of 60 carbon atoms arranged in a cage-like, fused ring structure consisting of 20 hexagons and 12 pentagons, and having a van der Waals diameter of about 1 nm. As such, Buckminsterfullerene is also a carbon nanoparticulate.

[0083] In any one more first embodiments herein, a paraffin suppressant composition comprises, consists essentially of, or consists of an admixture of a paraffin suppressant and about 0.001 wt % to about 1.000 wt %, in embodiments about 0.001 wt % to about 0.500 wt % of one or more nanoparticulates based on the weight of the paraffin suppressant, where the weight of the paraffin suppressant means the total weight of the one or more paraffin inhibitors, one or more paraffin dispersants, and one or more pour point depressants present in the composition. For example, a paraffin suppressant composition comprises, consists essentially of, or consists of a paraffin suppressant as described herein, admixed with 0.001 wt % to 1.000 wt % of one or more nanoparticulates based on the weight of the paraffin suppressant, often 0.001 wt % to 0.0500 wt %, such as 0.010 wt % to 0.500 wt %, or 0.020 wt % to 0.500 wt %, or 0.030 wt % to 0.500 wt %, or 0.040 wt % to 0.500 wt %, or 0.050 wt % to 0.500 wt %, or 0.060 wt % to 0.500 wt %, or 0.070 wt % to 0.500 wt %, or 0.080 wt % to 0.500 wt %, or 0.090 wt % to 0.500 wt %, or 0.100 wt % to 0.500 wt %, or 0.130 wt % to 0.500 wt %, or 0.150 wt % to 0.500 wt %, or 0.170 wt % to 0.500 wt %, or 0.200 wt % to 0.500 wt %, or 0.230 wt % to 0.500 wt %, or 0.260 wt % to 0.500 wt %, or 0.300 wt % to 0.500 wt %, or 0.320 wt % to 0.500 wt %, or 0.350 wt % to 0.500 wt %, or 0.370 wt % to 0.500 wt %, or 0.400 wt % to 0.500 wt %, or 0.420 wt % to 0.500 wt %, or 0.450 wt % to 0.500 wt %, or 0.470 wt % to 0.500 wt %, or 0.500 wt % to 0.600 wt %, or 0.600 wt % to 0.750 wt %, or 0.700 wt % to 0.900 wt %, or 0.750 wt % to 0.95 wt %, or 0.800 wt % to 1.000 wt %, or 0.001 wt % to 0.010 wt %, or 0.010 wt % to 0.020 wt %, or 0.020 wt % to 0.030 wt %, or 0.030 wt % to 0.040 wt %, or 0.040 wt % to 0.050 wt %, or 0.050 wt % to 0.060 wt %, or 0.060 wt % to 0.070 wt %, or 0.070 wt % to 0.080 wt %, or 0.080 wt % to 0.090 wt %, or 0.090 wt % to 0.100 wt %, or 0.100 wt % to 0.120 wt %, or 0.120 wt % to 0.150 wt %, or 0.150 wt % to 0.200 wt %, or 0.200 wt % to 0.250 wt %, or 0.250 wt % to 0.300 wt %, or 0.300 wt % to 0.350 wt %, or 0.350 wt % to 0.400 wt %, or 0.400 wt % to 0.450 wt %, or 0.450 wt % to 0.500 wt %, or 0.500 wt % to 0.550 wt %, or 0.550 wt % to 0.600 wt %, or 0.600 wt % to 0.650 wt %, or 0.650 wt % to 0.700 wt %, or 0.700 wt % to 0.750 wt %, or 0.750 wt % to 0.800 wt %, or 0.800 wt % to 0.850 wt %, or 0.850 wt % to 0.900 wt %, or 0.900 wt % to 0.950 wt %, or 0.950 wt % to 1.000 wt % of one or more nanoparticulates based on the weight of the paraffin suppressant.

[0084] In any one or more first embodiments herein, a paraffin suppressant composition is a paraffin suppressant concentrate, wherein the paraffin suppressant concentrate comprises, consists essentially of, or consists of an admixture of any one or more paraffin suppressants; any one or more of the nanoparticulates; and a solvent, wherein a solvent is a single compound or a mixture of two or more compounds, further wherein the compound or mixture thereof is substantially liquid within at least a portion of the range between 0 C. and 100 C. at 1 atm pressure. In some such embodiments, the solvent comprises, consists essentially of, or consists of one or more C1-C12 alkanols, one or more C5 to C16 linear alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or any of their cyclic or branched isomers or a mixture thereof; benzene, toluene, o-xylene, m-xylene, p-xylene, and mixtures thereof; methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol mono-methyl ether acetate, N,N-dimethyl acetamide, light aromatic naphtha, heavy aromatic naphtha, fuel oil, kerosene, or diesel. Naphtha is a petrochemical industry term describing boiling point fractions of petroleum distillate collected at different points on a distillation column. Naphtha fractions may include linear or branched or cyclic alkanes or alkenes, aromatic hydrocarbons, or fused ring aromatic compounds or mixtures of these materials. Light naphtha is lower boiling material collected near the top portion of the distillation column; medium naphtha higher boiling material from near the middle. Heavy naphtha, also called heavy aromatic naphtha or HAN, is an even higher boiling material from near the bottom portion of the column. A particularly useful HAN solvent is referred to as HAN 150, also known as Aromatic 150, sold by Univar Solutions of Downers Grove, IL; ExxonMobil of Spring, TX; and others.

[0085] In any one or more first embodiments herein, the solvent comprises, consists essentially of, or consists of an organic-ammonium salt of an alkylbenzene sulfonic acid, wherein the alkyl of the alkylbenzene is a C10 to C20 alkyl. In such embodiments, the solvent is a hydrotrope (also known as a phase transfer solvent). In some such embodiments, the hydrotrope comprises, consists of, or consists essentially of an organic-ammonium salt of the dodecylbenzene sulfonic acid having the formula V,

##STR00006##

wherein the organic-ammonium is selected from primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium functionalized with an organic group having 1 to 6 carbons. In embodiments, the organic-ammonium is ethanolammonium.

[0086] In embodiments herein, the one or more paraffin suppressants and one or more nanoparticulates of the paraffin suppressant concentrate are collectively referred to as actives, and the paraffin suppressant concentrate comprises, consists essentially of, or consists of an admixture of the actives with the solvent. In any one or more first embodiments herein, a paraffin suppressant concentrate includes about 1 wt % to about 90 wt % actives in a solvent, such as 1 wt % to 90 wt %, or 2 wt % to 90 wt %, or 3 wt % to 90 wt %, or 4 wt % to 90 wt %, or 5 wt % to 90 wt %, or 6 wt % to 90 wt %, or 7 wt % to 90 wt %, or 8 wt % to 90 wt %, or 9 wt % to 90 wt %, or 10 wt % to 90 wt %, or 12 wt % to 90 wt %, or 14 wt % to 90 wt %, or 16 wt % to 90 wt %, or 18 wt % to 90 wt %, or 20 wt % to 90 wt %, or 25 wt % to 90 wt %, or 30 wt % to 90 wt %, or 35 wt % to 90 wt %, or 40 wt % to 90 wt %, or 50 wt % to 90 wt %, or 60 wt % to 90 wt %, or 70 wt % to 90 wt %, or 80 wt % to 90 wt %, or 1 wt % to 80 wt %, or 1 wt % to 70 wt %, or 1 wt % to 60 wt %, or 1 wt % to 50 wt %, or 1 wt % to 45 wt %, or 1 wt % to 40 wt %, or 1 wt % to 35 wt %, or 1 wt % to 30 wt %, or 1 wt % to 25 wt %, or 1 wt % to 20 wt %, or 1 wt % to 15 wt %, or 1 wt % to 10 wt %, or 1 wt % to 5 wt %, or 1 wt % to 2 wt %, or 2 wt % to 3 wt %, or 3 wt % to 4 wt %, or 4 wt % to 5 wt %, or 5 wt % to 6 wt %, or 6 wt % to 7 wt %, or 7 wt % to 8 wt %, or 8 wt % to 9 wt %, or 9 wt % to 10 wt %, or 10 wt % to 12 wt %, or 12 wt % to 14 wt %, or 14 wt % to 16 wt %, or 16 wt % to 18 wt %, or 18 wt % to 20 wt %, or 20 wt % to 25 wt %, or 25 wt % to 30 wt %, or 30 wt % to 35 wt %, or 35 wt % to 40 wt %, or 40 wt % to 45 wt %, to 45 wt % to 50 wt %, or 50 wt % to 55 wt %, or 55 wt % to 60 wt %, or 60 wt % to 65 wt %, or 65 wt % to 70 wt %, or 70 wt % to 75 wt %, or 75 wt % to 80 wt %, or 80 wt % to 85 wt %, or 85 wt % to 90 wt % actives in a solvent.

[0087] In embodiments, the solvent comprises, consists essentially of, or consists of one or more non-aqueous solvents. In any one or more first embodiments herein, the solvent excludes or substantially excludes water. In any one or more first embodiments herein, a paraffin suppressant composition excludes a solvent. In any one or more first embodiments herein, the paraffin suppressant composition excludes a surfactant. In any one or more first embodiments herein, the paraffin suppressant concentrate excludes micelles. In any one or more first embodiments herein, the paraffin suppressant concentrate is characterized as a dispersion, and not an emulsion. In any one or more first embodiments herein, the paraffin suppressant composition is a paraffin suppressant concentrate characterized as an admixture of a paraffin suppressant, a nanoparticulate, and a solvent. In any one or more such embodiments, the solvent is a non-aqueous solvent; in some such embodiments, the paraffin suppressant concentrate includes 5 wt % water or less, often 4 wt % water or less, or 3 wt % water or less, or 2 wt % water or less, or 1 wt % water or less, such as 0-1 wt % water.

[0088] In any one or more first embodiments herein, a paraffin suppressant concentrate further includes a surfactant. In such embodiments, the paraffin suppressant concentrate is a paraffin suppressant emulsion. In any one or more first embodiments herein, a surfactant includes a single surfactant compound or a mixture of two or more surfactant compounds. In any one or more first embodiments herein, a paraffin suppressant emulsion is a paraffin suppressant microemulsion, that is, a clear, thermodynamically stable isotropic liquid mixture.

[0089] In any one or more first embodiments herein, a paraffin suppressant emulsion comprises, consists essentially of, or consists of one or more paraffin suppressants, one or more nanoparticulates, a solvent, and a surfactant. In any one or more first embodiments herein, a paraffin suppressant emulsion or a paraffin suppressant microemulsion includes one or more of: water, a surfactant, and/or micelles. In any one or more first embodiments herein, the surfactant comprises, consists essentially of, or consists of an oil-soluble surfactant having an HLB between about 6 and about 10, such as 6.0 to 6.5, 6.5 to 7.0, 7.0 to 7.5, 7.5 to 8.0, 8.0 to 8.5, 8.5 to 9.0, 9.0 to 9.5, or 9.5 to 10.0.

[0090] In embodiments, a paraffin suppressant emulsion or a paraffin suppressant microemulsion includes the same proportion of actives, and the same proportion of actives: solvent as a paraffin suppressant concentrates described above; and further includes an oil-soluble surfactant having an HLB between 6 and 10. In embodiments, a paraffin suppressant emulsion or a paraffin suppressant microemulsion includes about 5 wt % to about 30 wt % of the oil-soluble surfactant by weight of the paraffin suppressant composition overall, such as 5 wt % to 30 wt %, 5 wt % to 25 wt %, or 5 wt % to 20 wt %, or 5 wt % to 15 wt %, or 5 wt % to 10 wt %, or 10 wt % to 30 wt %, or 15 wt % to 30 wt %, or 20 wt % to 30 wt %, or 25 wt % to 30 wt %, or 10 wt % to 15 wt %, or 15 wt % to 20 wt %, or 20 wt % to 25 wt %, or 25 wt % to 30 wt % of the oil soluble surfactant based on the weight of the paraffin suppressant emulsion or paraffin suppressant microemulsion.

[0091] Examples of suitable oil soluble surfactants include alkylphenols having C9 or higher alkyl moieties; and dodecylbenzene sulfonic acid.

[0092] Optionally in any one or more paraffin suppressant compositions of first embodiments herein, the paraffin suppressant composition includes a fluorescent tracer for tracing the paraffin suppressant composition after addition thereof to one or more petroleum oils, as described below. A fluorescent tracer is a compound or material that fluoresces when irradiated and thereby provides means to measure the amount of another material present in a petroleum oil, in one or more locations, intermittently or continuously, in real time by irradiating the petroleum oil containing the fluorescent tracer with a wavelength of light known to cause a fluorescent emission from the tracer. The known fluorescence emission wavelength of the tracer is targeted for measurement. Accordingly, in some first embodiments herein, a fluorescent tracer is reacted with a paraffin suppressant to bond the tracer thereto, then the fluorescent paraffin suppressant is admixed with a nanoparticulate to form a fluorescent paraffin suppressant composition. In other first embodiments, a fluorescent tracer is admixed with a paraffin suppressant composition to provide a fluorescent paraffin suppressant composition. In such embodiments, the infrastructure targeted to contain or transport a petroleum oil stream having the fluorescent tracer dissolved or dispersed therein includes one or more fluorescence measurement modules, for irradiating the petroleum oil stream at a first wavelength and concomitantly measuring a fluorescence value at a second wavelength.

[0093] Fluorescent tracers particularly well suited for use in petroleum streams include graphene quantum dots having particle sizes of 2-20 nm, which obtain a fluorescent emission that is shifted away from the background emissions produced by petroleum oils when irradiated. Graphene quantum dots are carbon nanoparticles, as described above. The use of graphene quantum dots as fluorescent tracers, in mixtures with or covalently bonded to paraffin inhibitor polymers, is described in U.S. Pat. No. 10,233,273, the contents of which are incorporated herein in their entirety and for all purposes. Accordingly, in embodiments herein, a graphene quantum dot operates to obtain an improvement in paraffin suppression, and also operates as a fluorescent tracer.

[0094] Any one or more of the paraffin suppressants described herein are suitably reacted with a graphene quantum dot to covalently bond the graphene quantum dot to the paraffin suppressant, and thereby provide a fluorescently tagged paraffin suppressant. In some embodiments, a fluorescent paraffin suppressant composition comprises, consists essentially of, or consists of a tagged paraffin suppressant admixed with a nanoparticulate. Alternatively, a fluorescent paraffin suppressant composition comprises an admixture of a paraffin suppressant, a nanoparticulate, and graphene quantum dot having a particle size in the range of 2 nm to 20 nm, further as described in U.S. Pat. No. 10,233,273.

[0095] A graphene quantum dot bonded to a paraffin suppressant does not obtain an improvement in paraffin suppression, and functions solely or primarily as a means for quantifying the amount of a paraffin suppressant composition in a specified location, and do not function to inhibit paraffin precipitation or fouling, or lower the pour point of a petroleum oil to which the fluorescent paraffin suppressant composition is added. Accordingly, in any one or more of second through fifth embodiments below, a paraffin suppressant composition is suitably a fluorescent paraffin suppressant composition. The fluorescent paraffin suppressant composition can further include one or more graphene quantum dots that are not bonded to a paraffin suppressant, and such unbonded graphene quantum dots do obtain an improvement in paraffin suppression.

Second Embodiments

[0096] Disclosed in second embodiments herein are methods of forming a paraffin suppressant composition of first embodiments. In any one more methods of second embodiments, the methods include mixing any one or more paraffin suppressants described in first embodiments herein with any one or more nanoparticulates described in first embodiments herein, using concentrations, amounts, and mixing methods to obtain one or more paraffin suppressant compositions of first embodiments.

[0097] In any one or more second embodiments herein, the mixing comprises, consists essentially of, or consists of admixing a total of about 0.001 wt % to about 1.000 wt % of one or more nanoparticulates, with the one or more paraffin suppressants based on the total weight of the one or more paraffin suppressants. In any one or more methods of second embodiments, the methods comprise, consist essentially of, or consist of mixing one or more paraffin suppressants with one or more nanoparticulates, wherein one or both of the one or more paraffin suppressants and the one or more nanoparticulates are dispersed in a solvent.

[0098] In any one or more second embodiments herein, mixing is suitably accomplished using one or more conventional techniques for admixing polymers, oligomers, and/or small molecules such as surfactants with nanoparticulates to obtain an isotropic combination thereof.

[0099] Accordingly, any one or more methods of second embodiments herein suitably comprise, consist essentially of, or consist of dispersing one or more paraffin suppressants in a solvent to form a paraffin suppressant dispersion; and mixing one or more neat (solventless, or dry) nanoparticulates with the paraffin suppressant dispersion to obtain a paraffin suppressant concentrate of any of first embodiments herein. In any one or more such second embodiments, dispersing the paraffin suppressant to obtain a paraffin suppressant dispersion is accomplished using any one or more conventional techniques for obtaining an isotropic mixture of a paraffin suppressant in a solvent, such as paddle or blade mixing, shaking, adding heating, sonicating, and the like. In any one or more such second embodiments, the mixing of the one or more nanoparticulates with the paraffin suppressant dispersion is accomplished using static or dynamic methods, or a combination thereof. In some second embodiments, a paraffin suppressant is dispersed in a solvent by the manufacturer and/or during synthesis of the paraffin suppressant; in some such embodiments, the dispersion is used without modification for mixing of the one or more nanoparticulates while in other embodiments, some of the solvent is suitably removed e.g. by evaporation, and/or one or more additional solvent(s) are suitably added to a paraffin suppressant dispersion to obtain a desired concentration of paraffin suppressant in the solvent, and/or to obtain a desired viscosity of the dispersion for the mixing. In any one or more such embodiments, the mixing of the one or more nanoparticulates with the paraffin suppressant dispersion comprises, consists essentially of, or consists of one or more of: paddle or blade mixing, magnetic stirring, shaking, tumbling, rolling, swirling, adding heat, hand mixing, passing the admixture through a static mixing apparatus, sonicating, and applying a turbulent flow. In embodiments, the mixing obtains a paraffin suppressant concentrate that is an isotropic liquid mixture of the one or more paraffin suppressants in the solvent, further wherein the one or more nanoparticulates are isotropically suspended, or dispersed, throughout the isotropic liquid mixture of the solvent with the one or more paraffin suppressants.

[0100] Unexpectedly, we have found that dry nanoparticulates may be carefully admixed with paraffin suppressants in non-aqueous solvents to provide shelf-stable paraffin suppressant concentrates that are isotropic dispersions. Accordingly, in embodiments, the paraffin suppressants of first embodiments exclude water, or substantially exclude water; and further, no water is present and therefore no water needs to be removed from such a paraffin suppressant composition prior to use thereof to form the treated petroleum oils of fourth embodiments described herein below.

[0101] In any one or more second embodiments herein, the methods further include adding a surfactant to the solvent, and/or to the paraffin suppressant dispersion, prior to mixing the dry nanoparticulate with the paraffin suppressant dispersion to obtain the paraffin suppressant concentrate. In some such second embodiments, adding a surfactant having an HLB between 6 and 10, such as any of the surfactants described in first embodiments above, obtains a paraffin suppressant emulsion or microemulsion in accordance with first embodiments herein.

[0102] Alternatively, any one or more methods of second embodiments herein suitably comprise, consist essentially of, or consist of forming a nanoparticulate dispersion of one or more nanoparticulates in a solvent and mixing one or more neat paraffin suppressants with the nanoparticulate dispersion to form a paraffin suppressant concentrate. In embodiments, the nanoparticulate dispersion is a colloidal dispersion. In embodiments, the solvent excludes, or substantially excludes water, wherein substantially excludes means the solvent includes 5 wt % water or less. In embodiments, the nanoparticulate dispersion excludes, or substantially excludes water, wherein substantially excludes means the nanoparticulate dispersion includes 5 wt % water or less.

[0103] In any one or more second embodiments herein, the methods further include mixing a surfactant with the solvent, and/or with the paraffin suppressant concentrate, wherein such methods result in formation of a paraffin suppressant emulsion or microemulsion in accordance with first embodiments herein.

[0104] Alternatively, any one or more methods of second embodiments herein suitably comprise, consist essentially of, or consist of dispersing one or more paraffin suppressants in a first solvent to form a paraffin suppressant dispersion; dispersing one or more nanoparticulates in a second solvent to form a nanoparticulate dispersion; and mixing the paraffin suppressant dispersion with the nanoparticulate dispersion to form a paraffin suppressant concentrate. In some such alternative second embodiments, the first solvent and the second solvent are the same or are substantially the same, that is, the first and second solvents include 90% by weight of the same solvent (or mixture of solvents). In some such alternative second embodiments, the methods further include admixing a surfactant with the solvent, and/or with the paraffin suppressant dispersion, and/or with the paraffin suppressant concentrate, wherein such methods result in formation of a paraffin suppressant emulsion or microemulsion.

Third Embodiments

[0105] Also disclosed in third embodiments herein are methods of treating a petroleum oil, the methods comprising, consisting essentially of, or consisting of combining about 1 ppm to about 10,000 ppm by weight of any of the paraffin suppressant compositions of first embodiments with a petroleum oil, for example 1 ppm to 10,000 ppm, 1 ppm to 8,000 ppm, 1 ppm to 6,000 ppm, 1 ppm to 4,000 ppm, 1 ppm to 2,000 ppm, 1 ppm to 1,000 ppm, 1 ppm to 500 ppm, 1 ppm to 250 ppm, 1 ppm to 100 ppm, 1 ppm to 50 ppm, 1 ppm to 40 ppm, 1 ppm to 30 ppm, 1 ppm to 20 ppm, 1 ppm to 10 ppm, 1 ppm to 5 ppm, 0.1 ppm to 1 ppm, 10 ppm to 10,000 ppm, 100 ppm to 10,000 ppm, 1,000 ppm to 10,000 ppm, 2,000 ppm to 10,000 ppm, 3,000 ppm to 10,000 ppm, 4,000 ppm to 10,000 ppm, 5,000 ppm to 10,000 ppm, 6,000 ppm to 10,000 ppm, 7,000 ppm to 10,000 ppm, 8,000 ppm to 10,000 ppm, 9,000 ppm to 10,000 ppm, 5 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 200 ppm, 200 ppm to 300 ppm, 300 ppm to 400 ppm, 400 ppm to 500 ppm, 500 ppm to 600 ppm, 600 ppm to 700 ppm, 700 ppm to 800 ppm, 800 ppm to 900 ppm, 900 ppm to 1,000 ppm, 1,000 ppm to 2,000 ppm, 2,000 ppm to 3,000 ppm, 3,000 ppm to 4,000 ppm, 4,000 ppm to 5,000 ppm, 5,000 ppm to 6,000 ppm, 6,000 ppm to 7,000 ppm, 7,000 ppm to 8,000 ppm, or 8,000 ppm to 9,000 ppm by weight of any of the paraffin suppressant compositions of first embodiments with a petroleum oil. In any one or more third embodiments herein, the petroleum oil comprises, consists essentially of, or consists of a crude oil or a refined oil.

[0106] In any one or more third embodiments herein, a high paraffin petroleum oil includes at least about 3 wt % paraffin. In some embodiments, a high paraffin petroleum oil includes about 3 wt % to about 30 wt % paraffin, such as 3 wt % to 5 wt %, or 5 wt % to 10 wt %, or 10 wt % to 15 wt %, or 15 wt % to 20 wt %, or 20 wt % to 25 wt %, or 25 wt % to 30 wt % paraffin.

[0107] In any one or more third embodiments herein, the combining of the paraffin suppressant composition with the petroleum oil is accomplished using conventional methods for mixing paraffin suppressants with petroleum oils, often including e.g. injection at one or more points along a well production string carrying a crude oil; or within a refinery containment source for processing a petroleum oil; or within a refinery containment source for processing a refined oil, for example to reduce a pour point thereof by adding a pour point depressant thereto.

[0108] As noted above, some paraffin suppressant compositions of first embodiments exclude water, or substantially exclude water; in such embodiments, no water is present and no water needs to be removed from the paraffin suppressant composition prior to use thereof to form the treated petroleum oils of fourth embodiments herein. Accordingly, in some second embodiments, the methods of treating a petroleum oil suitably exclude drying a paraffin suppressant composition of first embodiments to remove water prior to combining the paraffin suppressant composition with a petroleum oil.

[0109] In embodiments where the paraffin suppressant composition is a paraffin suppressant concentrate or a paraffin suppressant emulsion or microemulsion, 10 wt %-99 wt % of the composition is solvent, as noted in first embodiments above; and the balance is actives. Accordingly, in any one or more third embodiments herein, combining 1 ppm to 10,000 ppm by weight of any of the paraffin suppressant compositions of first embodiments with a petroleum oil, is combining 0.01 ppm to 10,000 ppm by weight of actives with the petroleum oil, such as 0.01 ppm to 10,000 ppm, 0.01 ppm to 8,000 ppm, 0.01 ppm to 6,000 ppm, 0.01 ppm to 4,000 ppm, 0.01 ppm to 2,000 ppm, 0.01 ppm to 1,000 ppm, 0.01 ppm to 500 ppm, 0.01 ppm to 250 ppm, 0.01 ppm to 100 ppm, 0.01 ppm to 50 ppm, 0.01 ppm to 40 ppm, 0.01 ppm to 30 ppm, 0.01 ppm to 20 ppm, 0.01 ppm to 10 ppm, 0.01 ppm to 5 ppm, 0.1 ppm to 10,000 ppm, 1 ppm to 10,000 ppm, 10 ppm to 10,000 ppm, 100 ppm to 10,000 ppm, 1,000 ppm to 10,000 ppm, 2,000 ppm to 10,000 ppm, 3,000 ppm to 10,000 ppm, 4,000 ppm to 10,000 ppm, 5,000 ppm to 10,000 ppm, 6,000 ppm to 10,000 ppm, 7,000 ppm to 10,000 ppm, 8,000 ppm to 10,000 ppm, 9,000 ppm to 10,000 ppm, 0.01 ppm to 0.1 ppm, 0.1 ppm to 1 ppm, 1 ppm to 5 ppm, 5 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 200 ppm, 200 ppm to 300 ppm, 300 ppm to 400 ppm, 400 ppm to 500 ppm, 500 ppm to 600 ppm, 600 ppm to 700 ppm, 700 ppm to 800 ppm, 800 ppm to 900 ppm, 900 ppm to 1,000 ppm, 1,000 ppm to 2,000 ppm, 2,000 ppm to 3,000 ppm, 3,000 ppm to 4,000 ppm, 4,000 ppm to 5,000 ppm, 5,000 ppm to 6,000 ppm, 6,000 ppm to 7,000 ppm, 7,000 ppm to 8,000 ppm, or 8,000 ppm to 9,000 ppm, or about 10 ppm, about 50 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1,000 ppm, about 1,100 ppm, about 1,200 ppm, about 1,300 ppm, about 1,400 ppm, about 1,500 ppm, about 1,600 ppm, about 1,700 ppm, about 1,800 ppm, about 1,900 ppm, about 2,000 ppm, about 2,500 ppm, about 3,000 ppm, about 4,000 ppm, about 4,500 ppm, about 5,000 ppm, about 5,500 ppm, about 6,000 ppm, about 6,500 ppm, about 7,000 ppm, about 7,500 ppm, about 8,000 ppm, about 8,500 ppm, about 9,000 ppm, about 9,500 ppm, or about 10,000 ppm by weight of actives of a paraffin suppressant composition of first embodiments herein, in a petroleum oil.

Fourth Embodiments

[0110] Also disclosed in fourth embodiments herein are treated petroleum oils, the treated petroleum oils comprising, consisting essentially of, or consisting of a mixture of a petroleum oil with about 0.01 ppm to about 10,000 ppm actives by weight of a paraffin suppressant composition of first embodiments herein, such as 0.01 ppm to 10,000 ppm, 0.01 ppm to 8,000 ppm, 0.01 ppm to 6,000 ppm, 0.01 ppm to 4,000 ppm, 0.01 ppm to 2,000 ppm, 0.01 ppm to 1,000 ppm, 0.01 ppm to 500 ppm, 0.01 ppm to 250 ppm, 0.01 ppm to 100 ppm, 0.01 ppm to 50 ppm, 0.01 ppm to 40 ppm, 0.01 ppm to 30 ppm, 0.01 ppm to 20 ppm, 0.01 ppm to 10 ppm, 0.01 ppm to 5 ppm, 0.1 ppm to 10,000 ppm, 1 ppm to 10,000 ppm, 10 ppm to 10,000 ppm, 100 ppm to 10,000 ppm, 1,000 ppm to 10,000 ppm, 2,000 ppm to 10,000 ppm, 3,000 ppm to 10,000 ppm, 4,000 ppm to 10,000 ppm, 5,000 ppm to 10,000 ppm, 6,000 ppm to 10,000 ppm, 7,000 ppm to 10,000 ppm, 8,000 ppm to 10,000 ppm, 9,000 ppm to 10,000 ppm, 0.01 ppm to 0.1 ppm, 0.1 ppm to 1 ppm, 1 ppm to 5 ppm, 5 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 200 ppm, 200 ppm to 300 ppm, 300 ppm to 400 ppm, 400 ppm to 500 ppm, 500 ppm to 600 ppm, 600 ppm to 700 ppm, 700 ppm to 800 ppm, 800 ppm to 900 ppm, 900 ppm to 1,000 ppm, 1,000 ppm to 2,000 ppm, 2,000 ppm to 3,000 ppm, 3,000 ppm to 4,000 ppm, 4,000 ppm to 5,000 ppm, 5,000 ppm to 6,000 ppm, 6,000 ppm to 7,000 ppm, 7,000 ppm to 8,000 ppm, or 8,000 ppm to 9,000 ppm, or about 10 ppm, about 50 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1,000 ppm, about 1,100 ppm, about 1,200 ppm, about 1,300 ppm, about 1,400 ppm, about 1,500 ppm, about 1,600 ppm, about 1,700 ppm, about 1,800 ppm, about 1,900 ppm, about 2,000 ppm, about 2,500 ppm, about 3,000 ppm, about 4,000 ppm, about 4,500 ppm, about 5,000 ppm, about 5,500 ppm, about 6,000 ppm, about 6,500 ppm, about 7,000 ppm, about 7,500 ppm, about 8,000 ppm, about 8,500 ppm, about 9,000 ppm, about 9,500 ppm, or about 10,000 ppm by weight of actives of a paraffin suppressant composition of first embodiments herein, in a petroleum oil. In any one or more fourth embodiments herein, the petroleum oil comprises, consists essentially of, or consists of a crude oil or a refined oil. In any one or more fourth embodiments herein, the treated petroleum oil is an isotropic dispersion.

[0111] In any one or more fourth embodiments herein, the petroleum oil is a high paraffin petroleum oil that is, a petroleum oil having 20 wt % or more paraffin content, further wherein paraffins are defined to be hydrocarbon compounds having 18 or more carbons. In some such embodiments, the high paraffin petroleum oil is a high paraffin crude oil. In any one or more such embodiments, the treated petroleum oil is a treated high paraffin petroleum oil, such as a treated high paraffin crude oil.

[0112] The treated petroleum oils of fourth embodiments are characterized as having a pour point that is 0.1 C. to 10 C. lower than the pour point of the same petroleum oil, treated with the same amount of the same paraffin suppressant, but in the absence of the nanoparticulate, such as 0.1 C. to 0.2 C. lower, 0.2 C. to 0.3 C. lower, 0.3 C. to 0.4 C. lower, 0.4 C. to 0.5 C. lower, 0.5 C. to 0.6 C. lower, 0.6 C. to 0.7 C. lower, 0.7 C. to 0.8 C. lower, 0.8 C. to 0.9 C. lower, 0.9 C. to 1.0 C. lower, 1.0 C. to 1.2 C. lower, 1.0 C. to 1.4 C. lower, 1.4 C. to 1.6 C. lower, 1.6 C. to 1.8 C. lower, 2.0 C. to 2.2 C. lower, 2.2 C. to 2.4 C. lower, 2.4 C. to 2.6 C. lower, 2.6 C. to 2.8 C. lower, 2.8 C. to 3.0 C. lower, 3.0 C. to 3.2 C. lower, 3.2 C. to 3.4 C. lower, 3.4 C. to 3.6 C. lower, 3.6 C. to 3.8 C. lower, 3.8 C. to 4.0 C. lower, 4.0 C. to 4.2 C. lower, 4.2 C. to 4.4 C. lower, 4.4 C. to 4.6 C. lower, 4.6 C. to 4.8 C. lower, 4.8 C. to 5.0 C. lower, 5.0 C. to 5.2 C. lower, 5.2 C. to 5.4 C. lower, 5.4 C. to 5.6 C. lower, 5.6 C. to 5.8 C. lower, 5.8 C. to 6.0 C. lower, 6.0 C. to 6.2 C. lower, 6.2 C. to 6.4 C. lower, 6.4 C. to 6.6 C. lower, 6.6 C. to 6.8 C. lower, 6.8 C. to 7.0 C. lower, 7.2 C. to 7.4 C. lower, 7.4 C. to 7.6 C. lower, 7.6 C. to 7.8 C. lower, 7.8 C. to 8.0 C. lower, 8.0 C. to 8.2 C. lower, 8.2 C. to 8.4 C. lower 8.4 C. to 8.6 C. lower, 8.6 C. to 8.8 C. lower, 8.8 C. to 9.0 C. lower, 9.0 C. to 9.2 C. lower, 9.2 C. to 9.4 C. lower, 9.4 C. to 9.6 C. lower, 9.6 C. to 9.8 C. lower, or 9.8 C. to 10.0 C. lower, or two or more such ranges depending on the specific paraffin suppressant, nanoparticulate, and petroleum oil present in the treated petroleum oil. The treated petroleum oils of fourth embodiments are characterized as having a viscosity that is about 5% to about 50% lower at one or more points in the range of 60 C. and 4 C. than the viscosity of the same petroleum oil, treated with the same amount of the same paraffin suppressant, but in the absence of the nanoparticulate; for example, a viscosity that is 5% to 7% lower, or 7% to 9% lower, or 9% to 11% lower, or 11% to 13% lower, or 13% to 15% lower, or 15% to 17% lower, or 17% to 19% lower, or 19% to 21% lower, or 21% to 23% lower, or 23% to 25% lower, or 25% to 27% lower, or 27% to 29% lower, or 29% to 31% lower, or 31% to 35% lower, or 35% to 40% lower, or 40% to 45% lower, or 45% to 50% lower, or two or more such ranges depending on the specific paraffin suppressant, nanoparticulate, and petroleum oil present in the treated petroleum oil.

[0113] The treated petroleum oils possess the foregoing properties of improved viscosity and pour point without obtaining any bonding or grafting between the paraffin suppressant and the nanoparticulate and without surface functionalization of the nanoparticulate to obtain compatibilization of the nanoparticulate with the paraffin suppressant or with the petroleum oil. Furthermore, the treated petroleum oils are isotropic dispersions. It is an unexpected advantage to be able to admix nanoparticulates, especially nanoparticulates comprising or consisting essentially of highly polar compounds such as silica and alumina and aluminosilicate, with hydrocarbon compounds such as petroleum oils to provide isotropic mixtures. In the past, these materials have been considered to be incompatible, and an emulsion was required to combine them. The addition of water to a petroleum oil is undesirable, and accordingly Chinese application CN110922955A describes emulsion polymerization of octadecyl methacrylate, maleic anhydride, styrene, and acrylamide in the presence of a functionalized silica colloid, in order to graft polymerize an oil-soluble copolymer to silica, rendering the grafted silica oil dispersible and enabling the use of the polymer-grafted silica as a paraffin inhibitor. Emulsion polymerization obtains bonding of the hydrophobic monomers, such as octadecyl methacrylate, to the hydrophilic silica surface. However, the water must then be removed prior to adding the grafted material to a petroleum oil. Further, the grafting methodology is limited to those polymers suitable to obtain grafting to silica, and further are suitable for addition to an emulsion, or for emulsion polymerization, or for grafting to an aqueous colloidal particulate.

[0114] Unexpectedly, we have found that dry nanoparticulates and organosol type nanoparticulates may be carefully admixed with paraffin suppressants in non-aqueous solvents to provide shelf-stable paraffin suppressant concentrates that are isotropic dispersions. Accordingly, in embodiments, the paraffin suppressants of first embodiments exclude water, or substantially exclude water; and so no water is present and no water needs to be removed from such a paraffin suppressant composition prior to use thereof to form the treated petroleum oils of fourth embodiments herein. Accordingly, the treated petroleum oils of fourth embodiments are admixtures are easily formed using any paraffin suppressant, including those suited for graft polymerization as well as phenolic resins and polyethyleneimine polymers that are not suitable for graft polymerization to a nanoparticulate coupling agent, and/or are not suitable for use in aqueous emulsions as directed by CN110922955A to obtain compatibility of the silica nanoparticulate. Accordingly, any suitable paraffin inhibitor, paraffin dispersant, or even a pour point inhibitor that is non-polymeric may suitably be provided in a treated petroleum oil of fourth embodiments, since these admixtures also provide isotropic dispersions.

Fifth Embodiments

[0115] Disclosed in fifth embodiments herein is the use of any of the paraffin suppressant compositions of first embodiments herein to inhibit the precipitation of paraffin waxes in a petroleum oil or to disperse crystallized paraffin waxes in petroleum oil, by admixing a paraffin suppressant composition of first embodiments with a petroleum oil to form a treated petroleum oil of fourth embodiments. In any one or more fifth embodiments herein, the use further comprises subjecting the treated petroleum oil to a temperature of between 60 C. and 60 C., for example between 20 C. and 60 C., between 0 C. and 60 C., between 60 C. and 50 C., between 50 C. and 40 C., between 40 C. and 30 C., between 30 C. and 20 C., between 10 C. and 5 C., between 5 C. and 0 C., between 0 C. and 5 C., between 5 C. and 10 C., between 10 C. and 20 C., between 20 C. and 30 C., between 30 C. and 40 C., between 40 C. and 50 C., between 50 C. and 60 C., or any combination of these.

[0116] Also disclosed in fifth embodiments herein is the use of any of the paraffin suppressant compositions of first embodiments herein to inhibit the precipitation of paraffin waxes in a high paraffin petroleum oil or to disperse crystallized paraffin waxes in a high paraffin petroleum oil, by admixing a paraffin suppressant composition of first embodiments with a high paraffin petroleum oil to form a treated high paraffin petroleum oil of fourth embodiments.

[0117] Also disclosed in fifth embodiments herein is the use of any of the paraffin suppressant compositions of first embodiments herein to depress the pour point of a petroleum oil by forming a treated petroleum oil of fourth embodiments.

[0118] Also disclosed in fifth embodiments herein is the use of any of the treated petroleum oils of fourth embodiments for pumping and/or pouring at a temperature between 60 C. and 60 C., for example between 20 C. and 60 C., between 0 C. and 60 C., between 60 C. and 50 C., between 50 C. and 40 C., between 40 C. and 30 C., between 30 C. and 20 C., between 10 C. and 5 C., between 5 C. and 0 C., between 0 C. and 5 C., between 5 C. and 10 C., between 10 C. and 20 C., between 20 C. and 30 C., between 30 C. and 40 C., between 40 C. and 50 C., between 50 C. and 60 C., or any combination of these, further wherein the treated petroleum oil is pourable over a portion of the temperature range or over the entire temperature range.

[0119] Also disclosed in fifth embodiments herein is the use of any of the paraffin suppressant compositions of first embodiments herein to inhibit the precipitation of paraffin waxes in a petroleum oil or to disperse crystallized paraffin waxes in petroleum oil by forming a treated petroleum oil of fourth embodiments.

[0120] Also disclosed in fifth embodiments herein is the use of any of the paraffin suppressant compositions of first embodiments herein to inhibit the precipitation of paraffin waxes in a high paraffin petroleum oil or to disperse crystallized paraffin waxes in a high paraffin petroleum oil, by forming a treated high paraffin petroleum oil of fourth embodiments.

[0121] Also disclosed in fifth embodiments herein is the use of a graphene quantum dot having a particle size of 2 nm to 20 nm to quantify the amount of the paraffin suppressant composition present in a treated petroleum oil.

EXPERIMENTAL SECTION

Example 1

[0122] The following formulation were formed by admixing the recited components.

[0123] Control 1: A mixture of alkylphenol formaldehyde resins and ethoxylated nonylphenol resin was combined in a blend of toluene, xylene, and heavy aromatic naphtha (HAN) to provide a dispersion having 31 wt % toluene, 50 wt % HAN, 7 wt % xylene, 7 wt % alkylphenol formaldehyde resin, and 5 wt % ethoxylated nonylphenol resin, that is, 12 wt % actives.

[0124] Composition 1: A dry Halloysite nanoclay particulate (dry herein meaning having 5 wt % or less of any solvent) CAS No. 1332-58-7) was obtained from Sigma Aldrich; 0.05 wt % of the dry particulate was added to the Control 1 dispersion, based on the weight of the dispersion; and the admixture was sonicated.

[0125] Control 2: An alkyl ester copolymer was combined with HAN to provide a solution having 30 wt % actives in HAN.

[0126] Composition 2:0.10 wt % Halloysite nanoclay particulate (CAS No. 1332-58-7) was added to the Control 2 solution based on the weight of the solution; and the admixture was sonicated.

[0127] Control 3: An ethylene-vinyl acetate copolymer (CAS No. 24937-78-8) was combined with a mixture of liquid aromatic hydrocarbons having less than 1 wt % naphthalene to provide a dispersion having 4 wt % actives in an aromatic hydrocarbon solvent.

[0128] Composition 3:0.05 wt % Halloysite nanoclay particulate (CAS No. 1332-58-7) was added to the Control 3 solution based on the weight of the solution; and the admixture was sonicated.

[0129] Composition 4:0.10 wt % Halloysite nanoclay particulate (CAS No. 1332-58-7) was added to the Control 3 solution based on the weight of the solution; and the admixture was sonicated.

Example 2

[0130] Two crude oils were collected from Western Canada: one crude light oil collected from Montney; and one dark crude oil collected from the Cardium. The viscosity of the two oils in the absence of additives was measured using a Brookfield DV2T viscometer (obtained from AMTEK Brookfield of Middleboro, MA) starting at an initial temperature of 60 C. and reducing the temperature until maximum torque of the instrument was reached: 15 C. for the Montney oil, as shown in FIGS. 1 and 2; and 0 C. for the Cardium oil, as shown in FIGS. 3 and 4.

[0131] The Montney crude was dosed with 500 ppm by weight of Control 1 actives; or 500 ppm by weight of Composition 1 actives, and the viscosity measurements were repeated. The results of adding the Control 1 vs. Composition 1 treatments are shown in FIG. 1, further in comparison to the blank or untreated crude. As can be seen in FIG. 1, the addition of 500 ppm Composition 1 to Montney light crude oil obtained reduced viscosity over a broad range of temperatures at or below about 20 C., compared to the viscosity obtained by addition of 500 ppm of Control 1.

[0132] Similarly, the Montney crude was dosed with 3000 ppm by weight of Control 1 actives; or 3000 ppm by weight of Composition 1 actives, and the viscosity measurement was repeated. The results are shown in FIG. 2. As can be seen in FIG. 1, the addition of 3000 ppm Composition 1 to Montney light crude oil obtained reduced viscosity over a range of temperatures below about 2 C., compared to the viscosity obtained by addition of 3000 ppm of Control 1.

[0133] Then the Cardium dark crude oil was dosed with 500 ppm by weight of Control 1 actives; or 500 ppm by weight of Composition 1 actives, and the viscosity measurements were repeated. The results are shown in FIG. 3. As can be seen in FIG. 3, the addition of 500 ppm Composition 1 to Cardium crude oil obtained reduced viscosity over a broad range of temperatures at or below about 20 C., compared to the viscosity obtained by addition of 500 ppm of Control 1 to the Cardium crude.

[0134] Similarly, the Cardium crude was dosed with 1000 ppm by weight of Control 1 actives; or 1000 ppm by weight of Composition 1 actives, and the viscosity measurements were repeated. The results are shown in FIG. 4. As can be seen in FIG. 4, the addition of 1000 ppm Composition 1 to Cardium dark crude oil obtained reduced viscosity over a range of temperatures below about 15 C., compared to the viscosity obtained by addition of 1000 ppm of Control 1.

Example 3

[0135] Three crude oils were collected from Eastern Hemisphere: a condensate collected from the Caspian Sea; a condensate collected from the North Sea; and a light crude oil collected from the North Sea. Each of the crude oils was preheated at 60 C. for 1 hour; then applying the sample to a rotational pour point testing machine that determines pour point of oils in accordance with ASTM D5985-rotational method.

[0136] The pour point of the untreated Caspian condensate was found to be 8.9 C. Then an amount of the Caspian condensate was dosed with 200 ppm by weight of Control 2, and the pour point of the Control 2 mixture was measured and found to be 3.2 C. Then another amount of the Caspian condensate was dosed with 200 ppm by weight of Composition 2, and the pour point of the Composition 2 mixture was found to be 2.9 C., a decrease of 0.3 C. compared to Control 2.

[0137] The pour point of the untreated North Sea condensate was found to be 7.6 C. Then an amount of the North Sea condensate was dosed with 200 ppm by weight of Control 2, and the pour point of the Control 2 mixture was measured and found to be 1.4 C. Then another amount of the North Sea condensate was dosed with 200 ppm by weight of Composition 2, and the pour point of the Composition 2 mixture was found to be 2.1 C., a decrease of 0.7 C. compared to Control 2.

[0138] The pour point of the untreated North Sea light crude was found to be 4.7 C. Then an amount of the North Sea light crude was dosed with 500 ppm by weight of Control 3, and the pour point of the Control 3 mixture was measured and found to be 2.8 C. Then another amount of the North Sea light crude was dosed with 500 ppm by weight of Composition 3, and the pour point of the Composition 3 mixture was found to be 3.1 C., a decrease of 0.3 C. compared to Control 3. Finally, another amount of the North Sea light crude was dosed with 500 ppm by weight of Composition 4, and the pour point of the Composition 4 mixture was found to be 4.6 C., a decrease of 1.5 C. compared to Control 3.

Example 4

[0139] ORGANOSILICASOL MEK-ST was obtained from from Nissan Chemical. The organosol was 30 wt % silica in methyl ethyl ketone, <0.5 wt % water, 10-15 nm silica particle size as obtained. Ethylene glycol monobutyl ether (EGMBE) was added to the organosol to provide a 3 wt % silica organosol.

[0140] A polycarboxylate (R-60102, obtained from BASF of Ludwigshafen, Germany) was blended with toluene to form a 5 wt % solution; this solution was used as Control 4. Then a mixture of 85 wt % toluene, 10 wt % of the 3 wt % silica organosol, and 5 wt % [polycarboxylate R-60102] was admixed to provide Composition 5.

[0141] The Control 4 formulation was admixed at 250 ppm by weight actives (that is, 250 ppm of the polymer) with a crude oil collected from the Montney formation in Western Canada; and using a Brookfield DV2T viscometer the viscosity was measured starting at an initial temperature of 60 C. and decreasing to the temperature at which maximum instrument torque was observed (4 C. for the untreated oil sample).

[0142] Then Control 4 was added at 500 ppm to the crude oil and the viscosity was measured at the same temperature; and the percent reduction in viscosity over the 250 ppm mixture was determined to be about 3%. Then Control 4 was added at 1000 ppm to the crude oil and the viscosity was measured at the same temperature; and the percent reduction in viscosity over the 250 ppm mixture was determined to be about 6%.

[0143] Then the foregoing experiment was repeated except that Composition 5 was admixed with the crude oil at 250 ppm, 500 ppm, and 1000 ppm by weight of actives; and the resulting percent decrease in viscosity of each of these was compared to the 250 ppm mixture of Control 4 actives, as shown in FIG. 5. As can be seen in FIG. 5, at 250 ppm Composition 5 obtained a 6% decrease in viscosity compared to 250 ppm of Control 4. At 500 ppm Composition 5, the percent reduction in viscosity over the 250 ppm Control 4 measurement was determined to be about 21%, compared to 3% improvement going from 250 ppm Control 4 to 500 ppm Control 4: that is, an additional 18% improvement over Control 4. At 1000 ppm Control 5, the percent reduction in viscosity over the 250 ppm Control 4 measurement was determined to be about 30%, compared to 6% improvement going from 250 ppm Control 4 to 1000 ppm Control 4: that is, an additional 24% improvement over Control 4.