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 ºC 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 ºC and -4 ºC. 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.

Description

CHX0204WO (CXID24.27W0)PARAFFIN SI TPRFSSAN T ( AND METHODSTECHNICAL FIELD{00011 Crude oil is globally sourced from subterranean reservoirs using techniques such as drilling and hydraulic fracturing. As sourced from a reservoir, a crude oil typically includes linear, cyclic, and branched alkanes having the general formula CaH3n*2 wherein n is typically about 5-60, often 5-50; lower alkanes are produced from the reservoir as gases. Alkanes C5~ C 17 obtain a liquid phase over a range of use temperatures. However, higher molecular weight alkanes, such as Cl 8 (octadecane, melting point 28 - 30 °C) orC19 (nonadecane, melting point 33 °C) or higher linear alkanes have melting points that are greater than ambient or use temperatures in many cases. Some alkanes present in a crude oil can have melting points in excess of 60 °C. Accordingly, at temperatures of 60 "C and less, high melting alkane fractions in a crude oil can nucleate and crystallize, causing increased viscosity of the crude oil and / or precipitation of residue from the crude oil. The crystallized or precipitated residue is termed “paraffin” or “paraffin wax”.(0002] Transportation of crude oil products from a subterranean reservoir to a refining facility or other processing facility is accomplished by moving the crude oil through a conduit (such as a pipe) and into a containment for storage and / or transportation, such as a containment for storing and supplying the crude oil to one or more refining processes; or a containment associated with storage and transportation ofa crude oil via truck, railcar, ocean tanker, and the like. During the moving and / or storag e / transportation, the crude oil is often subjected to ambient temperatures between -40 °C and 60 °C, and accordingly paraffin residue is often deposited on the interior surfaces of conduits, and storage containments, and transportation containments carrying, or having carried, a crude oil. That is, paraffin tends to foul the interior surfaces of containments and conduits contacted by crude oil sources when a paraffin precipitate associates with and collects on the conduit or containment surface.{0003J The solidified paraffinic residue not only reduces the effecti ve volume of the structure within which it is contained, but also represents a loss of a valuable component from the body of the crude oil. Excessive paraffin wax buildup reduces the efficiency of transporting crude oil and leads to increased costs related to added downtime for cleaning of the pipes and / orvessels as well as disposal of residues removed from the vessel which increase environmental burdens. Further, some “high paraffin” crude oil sources inchide about 20 wt% or more, tsp to about 35 wt% paraffin content, which can solidify at one or more use temperatures to which the crude oil source is subjected after extraction from a subterranean reservoir. Such high paraffin crude oils are difficult to process due to significant paraffin fouling of surfaces contacted during the transportation and storage of the crude oil as well as surfaces contacted during processing thereof.

[0004] The precipitation of paraffin wax from a crude oil can be reduced by additives, called paraffin inhibitors, which interfere with the crystallization process of wax and / or obtain suspension or dispersion of wax crystals in the crude oil. Most paraffin inhibitors are polymeric. Examples of industrially useful paraffin inhibitors are copolymers of et hylene with one or more of vinyl acetate, acrylonitrile, or an a-olefln such as octene, butene, propylene, and the like; branched alkaryl condensation copolymers, such as alkylphenol formaldehyde copolymers; N- functioualized polyethyleneimines; and comb polymers having alkyl side chains, including alkylacrylamide, aciylate ester, and methacrylate ester homo* and copolymers in addition to “OMAC” copolymers, which are olefnvmaleate ester and olefln-maleimide copolymers.[0005| The deposition of paraffin wax from a crude oil source can also be reduced by additives, called “paraffin dispersants”, which operate not to prevent crystallization but rather to disperse wax and / or paraffin crystals that do form in the oil and thus also prevent paraffin deposition. Many paraffin dispersants are oligomeric or non-polymeric surfactan ts. Examples of paraffin dispersants include alkoxylated long-chain alkylphenols (c.g. ethoxylated or cthoxylated / propoxylaicd nonylphenol) and formaldehyde resins formed therefrom, alkylphenol formaldehyde resins, and ammonium salts of dodecyl benzene sulfonic acid (DDBSA). hi some cases, one or more paraffin dispersants are usefully combined with one or more paraffin inhibitors to provide more effective total treatment of foe paraffin present in the crude oil.

[0006] Prior to precipitation of paraffin from a crude oil, initial nucleation and growth of associated wax crystals causes the viscosity of the crude oil to increase; and this effect may be observed as a function of temperature. Accordingly, measuring the viscosity of a crude oil as a function of decreasing temperature provides as an effective technique to quantify the efficacy of a paraffin Inhibitor and / or a paraffin dispersant added thereto. Even after refining a crude oilio form one or more refined oils, viscosity of some refined oils can be observed to increase as a function of decreasing temperature. The lowest temperature at which a petroleum oik such as a crude oil or a refined oil, will pour (obtain gravity-induced flow) is its pour pointJ0007J Accordingly; “pour point depressants” is a term of art used in the industry to describe chemical additives used to facilitate the pumping, pouring, or other manipulation or use of petroleum oils at lower temperatures where the petroleum oil would otherwise have an unacceptably high viscosity, or even form a gel. Industrially, a pour point depressant is a chemical additive for reducing the pour point of refined oils, which can still form crystalline structures that result in increased viscosity - and even gel formation - at temperatures below about 20 °C, depending on the particular composition and properties of the specific petroleum oil. However, the pour point of a crude oil may be affected by the same crystallization mechanisms operable in connection with the pour point of a refined oil.|0008] Accordingly, in some cases, paraffin inhibitors and / or paraffin dispersants may also operate as pour point depressants in one or more petroleum oils selected from crude oils and refined oils. In a crude oil, mechanisms of inhibiting paraffin deposition or dispersing paraffin crystals that have formed may further operate to depress the pour point of the crude oil. Many commercially available pour point depressants have the same chemical composition as the paraffin inhibitor polymers listed above. Additionally, a limited number of nonpolymeric compounds based on fatty acid esters, such as pheuyitristeary'loxysilane pentaerythritol tetrastearate, are also effective pour point depressants.While these conventional chemical additive technologies for preventing hydrocarbon crystal formation and / or dispersing hydrocarbon crystals in petroleum oils have been known to work for many years, there remains a need in the industry for improved efficacy of such additives, for improved performance and / or allowing for an lower amount of the additive to be used while achieving a commensurate effect. Accordingly, there remains a need in the industry for compositions and methods for obtaining decreased precipitation and fouling by paraffins and higher alkanes present in petroleum oils, and / or decreased pour points in petroleum oils.SUMMARY|OQ10] Disclosed in first embodiments herein are paraffin suppressant compositions comprising, consisting essentially of, or consisting of one or more nanoparticulates combinedwith one or more paraffin suppressants. In any one more paraffin suppressant compositions of first embodiments herein, the paraffin suppressant comprises, consists essentially of, or consists of one or more paraffin inhibitors, one or more paraffin dispersants, one or more pour point depressants, or any mixture of two or more thereof. In any one more paraffin suppressant compositions of first embodiments herein, the nanoparticulate comprises, consists essen tially of, or consists of alumina, silica, or a mix ture thereof including any mixture of two or more different nanoparticulates. In any one more paraffin suppressant compositions of first embodiments, the paraffin suppressant composition includes about 0.001 wt% to about 1.000 wl% of the one or more nanoparticulates based on the weight of the paraffin suppressant composition, or based on the weight of the paraffin suppressant - that is, based on the weight of the one or more paraffin inhibitors, one or more paraffin dispersants, one or more pour point depressants, or mixture thereof.(0011] In any one or more first embodiments herein, a paraffin suppressant composition further includes a solven t admixed with the one or more nanoparticulates and the one or more paraffin suppressants in a dispersion. The solvent, is any single compound or any mixture of two or more compounds that is substantially liquid within at least a portion of the range between 0 °C and 100 °C at 1 atm. In any one or more first embodiments herein, a paraffin suppressant composition includes about 10 wt% to about 99 wt% solvent and about I wt% to about 90 wt% actives, that is, 1 to 90 total weight% of a combination of nanoparticulate(s) and paraffin suppressant(s) present in the solvent. In any one or more first embodiments herein, the solvent comprises an alkylene glycol moiioalkyl ether, a ketone, toluene, xylene, a heavy aromatic naphtha (HAN), a hydrotrope, or any combination thereof In any one or more first embodiments herein, the solvent excludes water. 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 composition excludes micelles. In any one or more first embodiments herein, the paraffin suppressant composition is not an emulsion. In any one or more first embodiments herein, the paraffin suppressant composition is characterized as a dispersion of a paraffin suppressant and a nanoparticulate in a nonaqueous solvent.(00121 In any one or more first embodiments herein, the paraffin suppressant composition includes an oil-soluble surfactant and / or a surfactant having an HLB between about 6 andabout 10. In any one or more such first embodiments herein, the paraffin suppressant composition is characterized as an emulsion or a microemulsion of a paraffin suppressant and a nanoparticulate.{0013] Also disclosed in second embodiments herein arc met hods of forming the para ffin suppressant compositions of first embodiments, wherein the methods of second embodiments 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 “near” (sol ventless, or dry) nanoparticulates with the paraffin suppressant dispersion to form a paraffin suppressant composition. Alternatively, in any one or more second embodiments herein, methods of forming a paraffin suppressant composition of first embodiments 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 composition. In some such alternative second embodiments, the first solvent and the second solvent are the same or are substantially the same. In any one or more second embodiments herein, the mixing comprises, consists essentially of or consists of mixing abou t 0,001 wt% to about 1 .000 wt% of the one or more nanoparticulates with the paraffin suppressant composition, based on the weight of the paraffi n suppressant.|0014] Also disclosed in third embodiments herein are methods of treating a petroleum oil. such as a crude oil or a refined oil, the methods comprising, consisting essentially of, or consisting of combining 0.01 ppm to 10,000 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. In any one or more third embodiments herein, the petroleum oil is a high paraffin crude oil.J0015] 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 by weight of a paraffin suppressant composition of first embodiments herein. In any one or more fourth embodiments herein, the petroleum oil comprises, consists essentially of or consists of a crude oi l or a refined petroleum oil.[0016| 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, for example 0,1 °C to iaC lower, or 1 °C to 2 °C lower, or 2 °C to 3 ~'C lower, or 3aC to 4 °C lower, or 4 °C to 5 °C lower, or 5aC to 6 °C lower, or 6CC to 7 ’"‘C lower, or 7 *C to 8 °C lower, or 8aC to 9 °C lower, or 9 “C to 10aC 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. The treated petroleum oils of fourth embodiments are characterized as having a viscosity that is 5% to 50% lower at one or more points in the range of 60 °C and -4aC than the viscosity of the same petroleum oil, treated with the same amount of the same paraffin suppressant, but in t he absence of the nanoparticulate, such as 5% to 10% tower, or 10% to 15% lower, or 15% to 20% lower, or 20% to 25% lower, or 25% to 30% lower, or 30% to 35% lower, or 35% to 40% lower, or 40% to 45% lower, or 45% to 50% lower at one or more points in the range of 60aC and -4 “C than the viscosity of the same petroleum oil, treated with the same amount of the same paraffin suppressant, but in tire absence of the nanoparticulate.[00171 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 petroleurn oil or to disperse crystallized paraffin waxes in petroleum oil by forming 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,JC and -20 °C, or between 20,JC and 0 °C. In any one or more fifth embodiments herein, the use farther comprises pumping and / or pouring the treated petroleum oil at a temperature between 60aC and -60aC, for example between 20and -20 °C, or between 20 °C and 0 °C.

[0018] Additional advantages and novel features of the invention will be set forth in part in the description that follows, and hi part will become apparent to those skilled in the art upon examination of the following, or may be learned through routine experimentation upon practice of the invention .BRIEF DESCRIPTION OF THE DRAWINGS j 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, j002®{ 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 2.10023] 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{00241 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 sei forth in this specification are not intended to be limiting and merely set forth some of the many possible embodiments for the appended claims.|0025j Definitions j0026{ 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, inchiding 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. jOt)27| The terms "comprise(s),” "include(s)," "having,” "has," "can," "containfs)," 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,I002S] 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 docs not,(0029| As used herein, the term "about" modifying, for example, the quantity of an ingredient m 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 I to 5” the recitation means “I to 5” and “about I to about 5” and “1 to about 5” and “about 1 to 5” unless specifically limited by context.(0030| A s 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 thatdoes not affect the overall recited composition, properly, quantity, method, position, value, or range thereof in a maimer 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 rhe 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 equi valents to these types and amounts of materials.

[0031] 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 arm.

[0032] 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 dissol ved or homogeneously dispersed therein.

[0033] 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.(0034] 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.

[0035] As used herein, the term “monomer” is tssed in context to mean either an unsaturated compound or the polymerized residue thereof (that is, a repeat unit).(00361 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.(0037] 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 CBRJKS-S, 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.J0038) As used herein, the term “petroleum oil” refers to a crude oil obtained from a subterranean reservoir or a refined (processed) oil derived tlierefrom, and including one or more hydrocarbons having the general formula GsHvs o that are liquid at 20CiC / l aim.(0039) 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 Cnllsn^ wherein n is 18 or greater. In some embodiments, n is 18-200, or 18- 150, or 18-100, or 18-60.(0040] 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.|90411 A s used herein, the term '‘paraffin suppressant” means one or more paraffin inhibitors, one or more paraffin dispersants, o»c or more pour point depressants, or a mixture of two or more thereof|0042| 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.|0043| As used herein, the term “paraffin dispersant.” means an oligomeric compound, a aon- 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.(0044) 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.

[0045] 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 I 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.

[0046] First Embodiments

[0047] 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

[0048] 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 a-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 mde%, 20 mole% to 25 mole%, 25 mole% to 30 mole%, 30 molc% to 35 molc%, 35 mofe% to 40 mole%, 40 molc% 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.

[0049] hi 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 io 4:5, 1: 1 io 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 cthylene-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: 1io 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 3:5.10050] As used in any one or more embodiments herein, the term “a-olefin” refers to an olefin (alkene) compound, or a repeal unit formed therefrom and present in a polymer or copolymer thereof, as determined by context. An a-olefin monomer has the general formula ( .'»H 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, ", 8, 9, 10, 1 1, 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 a-olefin compound is distinguished by having one double bond in the primary or alpha (a) position of the alpha-olefin molecule, i.e. the sole double bond in the molecule is between the first and second carbon atoms.(0051 ] Many a-olefins are available as mixtures of compounds with a distribution of lengths of the alkyl side chains. For example, a C10-C14 a-olefin in some embodiments is a mixture of alpha-olefins of various lengths of alkyl side chain, the CI0-C14 a-olefin having a number average distribution of chain lengths, wherein the distribution has a single number-maximum that lies at from C 10 to C 14. Therefore the term “an a-olefin” herein also refers to a mixture of a-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 “a- olefms” refers to a mixture of a-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.|0052] In some such embodiments, an ethylene - a-olefin copolymer includes a mole ratio of ethylene to the total of the one or more a-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 : 10.10053] Further in any one more paraffin suppressant compositions of first embodiments, suitable paraffin inhibitor polymers include alkaryi condensation copolymers, such asalkylphenol -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 aikylphenol monomer is a substituted phenol having formula I,wherein the substituent R.!is a hydrocarbyl group selected from C1-C60 alkyl and C1 -C60 alkaryl, and is often C6-C18 alkyl In some embodiments, R!is or includes C9 (nonyl). In some embodiments, R L is attached to the para position of the alkylphenol. When subjected to conventional condensation conditions in the presence of formaldehyde, the aikylphenol, optionally further including phenol, resorcinol or another substituted phenolic compound, forms a heavily branched paraffin inhibitor polymer.|0054] Further in any one more paraffin suppressant compositions of first embodiments, suitable paraffin inhibitor polymers include N-functionalized polyethyleneimines, which arc polymers having a structure -4.CH2-CH2-NR2|m~| CHz-Clh-NIdjn- 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 uni Is is 1: 1 or greater; and R2is a C 1 -C60 linear or branched hydrocarbyl group, such as a Cl , C2, C3, C2-C4, C3-C5, C4-C6, C5-C7, C7-C9, C8-C 10, C10-C14, C11-C13, C12-C14, CI3-C15, C.14-C16, C15-C17, C16-C.18, C17-C19, C18-C20, C20-C22, C22-C24, C24-C26, C26-C28, C28-C30, C30-C40, C40-C50, or C50-C60; further wherein R?is the same or different for each in repeat unit. In some such embodiments, the N- fimcdonalized polyethyleneimine is linear; in other embodiments, the N-funetionalized polyethyleneimine is branched.|0055| 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 alkylacryiamide, acrylate ester, and methacrylate ester homo- andcopolymers; and “OMAC” copolymers, which are olefm-maleate ester and olefin-nialcimide copolymers.{0056) Acrylate comb polymers are synthesized using conventional additional polymerization methodology and comprise, consist essen tially of, or consist of homopolymers and copolymers of monomers having the formula II,wherein R', R4, and R' are individually selected from hydrogen and methyl; and X is selected from NHR*' and OR'’. wherein R6is a C5-C60 linear or branched hydrocarbyl group, such as a C5-C7, C7-C9, C8-C10, C10-C14, CH -Cl 3, CI2-C14, C13-C15, C14-CI6, C15-C17, Cl 6- C18, CI7-C.19, 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 11 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 arc further copolymeriz.ed with ethylene or an olefin, such as an a-olefin, including any one or more of the C3-C50 a-olefins described above.{00571 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-viny l ester polymers are described in WO 2014 / 095412,|0058| 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 asethylene or any one or more of the a-olefins described above, with a maleimide in accordance with formula III,wherein R' and R* are individually selected from hydrogen and C1-C50 alkyl and R9is a C5 to C60 hydroearbyl group, such as a C5-C7, C7-C9, C8-C10, C10-C14, Cl 1-CI3, C12-C14, C13-C15, C14-C16, C15-C17, C16-C18, CI7-C19. CJ 8-C2O, C20-C22, C22-C24, C24-C26, C26-C28, C28-C30, C30-C40, C4O-C5O, C50-C60 hydrocarbyl group that is a linear or branched alkyl, alkenyl, alkaryl, or aralkyl group. In embodiments, at least one of R7and Rsis hydrogen. In embodiments, both R;andR* are hydrogen. In some embodiments, the OMAC comb copolymer includes the polymerized residue of one or more amide monomers in accordance with formula Ilia,wherein R;, Rs, and Rvare the same as in formula III; and X’ is NHR*fN(R8)y OR\ or OH or a conjugate base thereof.J0059| In some embodiments, an OMAC comb copolymer includes more than one a-olefm copolymerized therewith. In some such embodiments, the OMAC comb copolymer includes the polymerized residues of two or more of: a C12-C16 a-olefin; a C17-CI9 a-olefm; a C22- C32 a-olefin; and a C32-C52 a-olefin, further as described in US Patent No. 10,738,138. j00601 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, inembodiments 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.J0061.J 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.|0062J 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.|0063] In any one more paraffin suppressant compositions of first embodiments, suitable paraffin dispersants include ammonium dodecyl benzene sulfonic acid (DDBSA) and alkoxy lated alcohols. In some such embodiments, suitable alkoxylated alcohols inchide ethoxylated C5 to C60 alkanols, propoxy lated C5 to C60 alkanols, and ethoxylated / propoxylated C5 to C60 alkanols comprising a random, block, or alternating copolymer of ethylene oxide and propylene ox ide.J0064| In any one more paraffin suppressant compositions of first embodiments, suitable paraffin dispersants are selected from alkoxyiated alcohols having formula IV,wherein RK>is hydrogen or C 1 -C6 alkyl group, R5 !is a linear or branched C5-C5O hydrocarbyl group, such as a C5-C7, C7-C9, C8-C10, CI0-C14, Cl 1-C13, C12-C14, C13-C15, C14-C16, C15-C17, CI6-C18, C17-C19, C18-C20, C20-C22, C22-C24, C24-C26, C26-C28, C28-C30, C30-C40, C4O-C5O, 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 ofp+q is 1 to 200, such as 1 to 3, 3 to 5, 5 to 7, 7 to 9, 9 to 1 1 , 1 1 to 13, 13 to 15, 15 to 20, 20 to 2.5, 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 1 10, HO 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,|0065| 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 ox ide, 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 magnesi trm-zinc, magnesi trm-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 alkoxyiated 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, lor example, in US Patent .Nos. 5,750,796; 7,335,235; and 8,524,643.(0066| 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 typefs) 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 : J 00, or 100: 1 to 1 :40, or 30: J to J : 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: J to J : 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; I 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 a bout 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 :3(), or about 1 :40, or about 1 :50, or about 1 : 100.|0067( 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.J0068J In any one more paraffin suppressant compositions of first embodiments, suitable pour point depressants further include carboxy and siloxy esters. Carboxy faty esters have the formula RU-COOR1-’ wherein Ruis a C10-C50 alkaryl, aralkyl, alkyl, or alkenyl group, and R° 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 (Ri4):Si(C)RS5)4< wherein r is 1 , 2, or 3, and R14and R15areindependently selected from C5-C50 alkaryl, aralkyl alkyl or alkenyl groups. One useful example of a siloxy ester pour point depressant is phenyliristearyloxy silane .10069) 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 effecti vely 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.|O07O| 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 volumebased method such as light scattering. In some paraffin suppressant compositions of first embodiments herein, the mmoparticulate comprises, consists essentially of, or consists of two or more discrete groups of different nanoparticles, or nanopardcle species, wherein the two ormore 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

[0071] 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 aluntina-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.1'0072} 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 m2 / g to about 1500 m’ / g, such as 100 nr’ / g to 1500 nri / g, or 200 nri / g to 1500 nri / g, or 300 m2 / g to 1500 m* / g, or 400 nri / g to 1500 m-7g, or 500 m2 / g to 1500 nri / g, or 600 nri / g to 1500 nri / g, or 700 nri / g to 1500 nri / g, or 800 m2 / g to 1500 m2 / g, or 900 nri / g to 1500 nri / g, or 1000 nri / a to 1500 nri / e, or 1100 iiri / g to 1500 m2 / g, or 1200 nri / g to 1500 m2 / g, or 1300 nri / g to 1500 nri / g, or 1400 nri / g to 1500 nri / g, or 20 nri / g to 1200 m2 / g, or 20 nri / g to 1000 nri / g, or 20 nri / g to 900 m2 / g, or 20 nri / g to 800 m2 / g, or 20 nri / g to 700 nri / g, or 20 m2 / g to 600 m2 / g, or 20 nri / g to 5CX) nri / g, or 20 nri / g to 400 nri / g, or 20 nri / g to 300 nri / g, or 20 nri / g to 200 nri / g, or 20 nri / g to 100 nri / g, or nri / g to 50 nri / g, or 50 nri / g to 1 (X> nri / g, or 100 nri / g to 200 nri / g, or 200 nri / g to 300 nri / g,or 300 m2 / g to 400 m-7g, or 400 m2 / g to 500 m2 / g, or 500 nr7g to 600 tnvg, or 600 nr / g to 700 nr7g, or 700 m- / g to 800 nr / g, or 800 nr / g to 900 nr / g, or 900 m2 / g to 1000 m2 / g, or 1000 m~ / g to I iOO ni2 / g, or 1 100 tn 7g to 1200 m2 / g, or 1200 m2 / g to 1300 m2 / g, or 1300 m2 / g to 1400 m2 / gtor 1400 m7g to 1500 mCg,10073] hi 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 I 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 tun - 50 nm, or 1 nm -IO 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 imi - 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 mn ~ 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 am , or 110 nm ~ 120 nm, or 120 nm -■ 130 nm, or 130 nm - 140 nm, or 140 tun 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 I 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 am to 300 nm, or 300 ntn - 350 nm, or 350 nm - 400 nm, or 400 nm 450 nm, or 450 nm 500 nm, or 500 nm - 600 tnn, or 600 am - 700 nm, or 700 nm - 800 nm, or 800 nm - 900 nm when measured using light scattering.(00*741 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 finned 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 20(1 nm. Fumed silica is anamorphous, 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 mn, providing a surface area of 50 m2 / g -600 nr / g.

[0075] 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 tun and 1000 nm. between 5 nm and 500 am, or between 5 nm and 200 nm. Non-aqueous silica nanoparticle dispersions are also available synthetically or commercially. Commercially, silica nanoparticle dispersions arc 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.(00761 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, tor example I nm - 200 nm, or 1 nm - 150 nm, or 1 nm - 100 nm, or I nm - 50 nm, or 1 nm - 20 nm, or I tun -- 10 nm, or 10 nm - 20 nm, or 20 tun -- 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 Bioparticlcs of Shirley, NY; or under the trade name LE VASILI 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 ami Surfrces A: PftyskwftemfoaZ and Engineering Aspects Volume 441,pp. 170-177 (2014) or Chen et al., Cmraicr toemt / tat / Volume 46, Issue I, pp. 196-203 (2020).J0077| In say 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.d Si4)ie(0H):?]), vermiculite (similar to talc but including additional layers of water molecules), mica (KAh[AlSbOuKOH)2 ]), kaolin (Ah(SizO$(OH)4]), montmorillonite (Mgo.33Ali.6?[Si40us(OH)i| (Ca, Na> (HjO)i:), serpentine (Mg^SisOsf'OHXl) and sepiolite (Mg-^SisOtsKOH)? 41-ftO) 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.|0078) One example of a useful nanoclay is halloysite, (AhSisCXOHJ-rtSHzOX a layered nanotube that is chemically similar to kaolin and ha ving CAS No. 1332-58-7. A nanotube is a discrete particulate structure having a hollow cylindrical morphology with a cylinder outer diameter of I 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.(00791 Since they are natural materials, halloysite particle dimensions are variable. In embodiments, the length of a halloysite nanotube cylinder ranges from 10 nanometers to) to 10 microns (gm), most often about 100 nm to about 2 gm, 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 A 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 walers of hydration cause a natural curving or curling to result in a characteristic cylindrical morphology having different chemistries on the inner and outer surfaces thereofIn 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 t hese.(0081) 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 acti vated carbon is deri ved 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 m3 / g, often 1000 mzZg or greater, or 2000 nrv'g or greater, or even 3000 m2 / g or greater. In embodiments, an activated carbon particulate is macroporous, nanoporous, microporous, or mcsoporous. 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.|OO82] 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 I mn to about 20 nm, such as about 1 nm, about 2 lim, 3 about mn, about 4 nm. about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm. about 1 1 nm. about 12 nm, about 13 nm, about 14 nm, about 15 nm, about 16 nm, about 17 nm, about 18 nm, about 19 am, or about 20 nm. Depending on the method of preparation, one or more functional groups may be bonded to the GQD at the cdge(s) thereof, wherein any one such functional group comprises or consists of one or more hydroxyl, carbonyl, carboxyl, amino, amido, mercapto, or hydrocarbyl groups.Carbon nanotubes arc singly-layered graphene sheets in cylindrical form, typically having a cylinder height ranging from about I nm to several microns, and inner diameters of about 0.5 um 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 urn, about 1 . 1 nm, about 1,2 nm, about 1 .3 nm, about 1.4 nm, about 1 .5 tun, about 1.6 nm, about 1.7 tun, about 1.8 nm, about 1.9 mn, or about 2,0 nm. Depending on the method of preparation, one or more functional groups may be bonded to a carbon nauolube 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 nanombes are annularly nested single-wall carbon naaotubes. Double- and triple-walled carbon nanotubes are known.(00841 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 Wash diameter of about I urn, As such, Bucknitnstcrftdlcrenc is also a carbon nanoparticulate.(0085] 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 wi% 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 suppressan t, whe re 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 nanopartic ulates 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 wi% 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 wi% to 0.500 wt%, or 0.450 wt% to 0.500 wi%, 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 wl%, or 0.020 wi% to 0.030 wt%, or 0.030 wi% to 0.040 wi%, 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 wi% 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 vvt%, 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 wl% to 0.650 wt%, or 0.650 wi% 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 0.950wC4, or 05)50 wt% to .1 .000 wt% of one or more nanoparticulates based on the weight of the paraffin suppressant.|0086] 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 I atm pressure, la some such embodiments, the solvent comprises, consists essentially of. or consists of one or more Cl -C 12 alkanols, one or more C5 to C 16 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-xyleue, w-xylene, / i-xylcnc, 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-dimeihyl 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.J0087 j 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 CI O 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 orgamc-ammoniunt salt of the dodecylbenzene sulfonic acid having the formula V,V 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 ethanolammomum.|0088| In embodiments herein, the one or more paraffin suppressants and one or more nanoparticulates of the paraffin suppressant concentrate are collecti vely 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 I 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 wi%, 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 wi% 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 wl%, 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 J wt% to 60 wt%, or 1 wt% to 50 wt%, or 1 wt% to 45 wt%, or 1 wt% to 40 wt%, or I wt% to 35 wt%, or 1 wt% to 30 wt%, or i wt% to 25 wt%, or 1 wt% to 20 wt%, or 1 wt% to 15 wt%, or 1 wt% to 10 wt%, or I wt% to 5 wt%, or I wt% to 2 wi%, or 2 wi% 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 30wi% to 35 w(%, or 35 wt% to 40 wt%, or 40 w(% io 45 wt%, o 45 wt% to 50 vvt%, 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 wf’o actives in a solvent.10089] 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 wi% water or less, or 2 wt% water or less, or I wt% water or less, such as 0-1 wt% water.(0t>90| 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. Ln 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. J00911 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 anHLB 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.[0092| 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% io 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,10093] Examples of suitable oil soluble surfactants include alkylphenols having C9 or higher alkyl moieties; and dodecylbenzene sulfonic acid.

[0094] 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 fight 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 io 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 io 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 petroleuni oil stream at a first wavelength and concomitantly measuring a fluorescence value at a second wavelength.(0095| Fluorescent tracers particularly well suited for use in petroleum streams include graphene quantum dots having particle sizes of 2-20 am, 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. Patent No. 10,233,273, the contents of which are incorporated herein in their entirety and for ail purposes. Accordingly, in embodiments herein, a graphene quantum dot operates to obtain an improvement in paraffin suppression, and also operates as a fluorescent tracer.|00%| Any one or more of the paraffin suppressants described herein are suitably reacted with a graphene quantum clot 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 lagged 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 run, further as described in U.S. Patent No. 10,233,273.|0097j 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.|O098]| Second Embodiments

[0099] 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 infirst 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.(0U>0| In any one or more second embodiments herein, the mixing comprises, consists essentially of or consists of admixing a total of about OXXll wt% to about 1 .000 wl% 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 essen tially of, or consist of m ixing 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 |0101| 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.10102] 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 healing, sonicating, and the like. In any one or more such second embodiments, the mixing of the one or more nanoparticulates with die 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 c.g, by evaporation, and / or one or more additional solvents) 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 thedispersion 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.JO 1031 Unexpectedly, we have found that dry nanoparticulates may be carefully admixed with paraffin suppressants in non-aqueous solvents to provide shell- 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.[O104| 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. JO105] 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.(0106| 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. f 0107] 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 sol vent 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.(0108| Third Embodiments}0109j 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, 0(X) 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 6,0(X) ppm, I ppm to 4,000 ppm, I ppm to 2,000 ppm, 1 ppm to 1,000 ppm, 1 ppm to 500 ppm, 1 ppm to 250 ppm, I 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 io 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 io 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.(0110] 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. (011'1] hi any one or more third embodiments herein, t he combining of the paraffin suppressant composition with the petroleum oil is accomplished using conventional methods tor 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.J011.2] 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.JO 113] hi 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, 0.01ppm to 4.000 ppm, 0.01 ppm to 2,000 ppm, 0.01 ppm io 1 ,000 ppm, 0.0.1 ppm to 500 ppm. 0..01 ppm io 250 ppm, 0.01 ppm io 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, (XX) 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 io 1 ppm, 1 ppm to 5 ppm, 5 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm io 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 io 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.J0114| Fourth EmbodimentsJ01 15| 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 1.0,000 ppm,100 ppm to .10,000 ppm, 1 ,000 ppm to 10,0(10 pp.m, 2,000 ppm to 10,000 ppm, 3,000 ppm to 10,000 ppm. 4,000 ppm io 10,000 ppm, 5,000 ppm io 10,000 ppm, 6,000 ppm io 10,000 ppm, 7,000 ppm io 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 I 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 io 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, about1.500 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 6,50(1 ppm, about 7,000 ppm, about7.500 ppm, about 8,000 ppm, about 8,500 ppm, about 9,00(1 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.{0116| 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 ,(01171 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 *€ lower, 0.2 *€ to 0.3 *C lower, 0.3 °C to 0.4 °C lower, 0.4 °C io 0.5 °C lower, 0.5 X to 0.6 °C lower, 0.6 X to 0.7aC lower, 0.7aC to 0.8aC lower, 0.8aC to 0.9aC tower, 0.9aC to 1 .0aC tower, 1 .0aC to 1 .2aC tower, 1 .0 °C to 1 .4°C lower, 1 ,4 °C to 1.6 °C tower, 1 .6aC to 1 .8 °C tower, 2.0 °C to 2.2 °C lower, 2.2 °C to 2.4 °C lower, 2.4 °C to 2.6 °C tower, 2.6aC to 2,8 °C lower, 2,8aC to 3.0aC lower, 3.0aC to 3.2aC lower, .3.2aC 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 4,2aC lower, 4.2aC 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 tower, 5.4 °C to 5.6 °C lower, 5.6 °C to 5.8 *C lower, 5.8aC to 6.0aC lower, 6.0aC to 6.2aC lower, 6.2aC to 6.4aC lower, 6.4aC to6.6aC 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 to7.6 °C lower, 7.6 °C to 7.8 °C lower, 7,8 °C to 8,0 °C tower, 8,0 °C to 8,2 °C tower, 8,2 °C to 8.4 °C lower 8.4 ®C to 8.6 ®C lower, 8.6 ®C to 8.8SC lower, 8.8 ®C to 9.0 ®C lower, 9.0SC to 9.2 "C lower, 9.2aC to 9,4aC lower, 9,4°C to 9.6 °C lower, 9.6 °C to 9,8 °C lower, or 9.8aC to 10.0aC 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 al 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 1 1% lower, or 1 1% to 13% lower, or 13% to 15% lower, or 15% to 17% lower, or 17% to 19% tower, or 19% to 21% tower, or 21% to 23% lower, or 23% to 25% lower, or 25% to 27% tower, or 27% to 29% tower, or 29% to 31 % lower, or 31 % to 35% lower, or 35% to 40% tower, 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.{0118] 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 t he petroleum oil. Furthermore, the treated petroleum oils are isotropic dispersions. It is an unexpected advantage to be able to admix nanoparticulates, especially nanoparticulates comprising orconsisting 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 CNl 10922955A 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 io 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.(Oil 9| 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 o il of fourth embodiments, since these admixtures also provide isotropic dispersions.|01 ~0| Fifth EmbodimentsJOI 211 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 fi rst embod iments 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 - 60CC, for example between 20 "C and -60 “C, between 0 "C and - 60 °C, between 60 °C and 50CC, between 50 *C and 40qC, between 40 ~'C and 30qC, 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 -10VC and -20 °C, between -20 “C and -30CC, between -30 "C and -40 “C, between -40 °C and -50 °C, between -50,JC and -60 °C, or any combination of these.|O122j Also disclosed in fifth embodiments herein is the use of any of the paraffin s uppressant composition s 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 Heated high paraffin petroleum oil of fourth embodiments.|0123] 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.(0124| 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 -60between 0 °C and - 60 '’C, between 60 °C and 50CC, between 50 °C and 40 °C, between 40 "C and 30 °C, between 30 "C and 20 "C, between 10 "C and 5CC, between 5 “C and 0 °C, between 0 °C and -5 °C, between -5 °C and - 10QC, between -10 ~'C and -20 °C, between -20and -30 ~'C, between -30QC and -40between -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.[0125| 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,[0126) 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, f 0127} 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,[0128| EXPERIMENTAL SECTION[0129| Exampie 1 f0130] The following formulation were formed by admixing the recited components.[(11311 Cowzrad Z : 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.

[0132] Campaw / km I: 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 wi% of the dry particulate was added to the Control I dispersion, based on the weight of the dispersion; and the admixture was sonicated.[01331 Control 2; An alkyl ester copolymer was combined with HAN to provide a solution having 30 wt% actives in HAN,(0134] Composition 2: 0.10 wt% Halloysite nanoclay particulate (CAS No. 1332-58-7) was added to the Control 2 sol ution based on the weight of the solution; and the admixture was sonicated.(0135| CoMroZ 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.(01361 Camposilion 3: 0.05 wt% Halloysite nanoday particulate (CAS No. 133.2-58-7) was added to the Control 3 solution based on the weight of the solution; and the admixture was sonicated.(0137] 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,J0138] Example 2(0139] 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 Middlcboro, 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 lor the Cardium oil, as shown in FIGS, 3 and 4.(0140] 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 I vs. Composition 1 treatments are shown in FIG. 1, further hi 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 I .(01411 Similarly, the Montney crude was dosed with 3 (XX) 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 oftemperatures below about 2 °C, compared to the viscosity obtained by addition of 3000 ppm of Control I. j0142j Then the Cardium dark crude oil was dosed with 500 ppm by weight of Control i 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 I 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.JO 143 ] Similarly, the Cardium crude was dosed with 1000 ppm by weight of Control I 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 I 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 .J0144| Exampk 310145] 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. j0146j 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 Cornposition 2 mixture was found to be 2.9CC, a decrease of 0.3 *C compared to Control 2.J0147| 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 anotheramount 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 0.7compared to Control 2.10148] 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 -2.8c;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 mix ture 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.|0I49| Example 4(0150) ORCn4NOSILiCASOL® MEK-ST was obtained from from Nissan Chemical. The organosol was 30 wt% silica in methyl ethyl ketone, < 0.5 wt% water, 10-15 ran silica particle size as obtained. Ethylene glycol monobutyl ether (EGMBE) was added to the organosol io provide a 3 wt% silica organosol.|0151] A polycarboxylate (R-60102, obtained from BASF of Ludwigshafen, Germany) was blended with toluene io 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.J0152| 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 Monmey 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).(0153] 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 theviscosity was measured at the same temperature; and the percent reduction in viscosity over the 250 ppm mixture was determined to be about 6%.J0154| 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 J 8% 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.

Claims

1. CLAIMS:

1. A paraffin suppressant composition comprising a mixture of: a paraffin suppressant and0.010 wt% to 1,000 wt% of a nanoparticulate based on tire 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 composi tion of claim 1 , claim 2, or claim 3 further comprising a solvent, the solvent comprising one or more C 1 -C12 alkanols, one or more linear, branched, or cyclic C5 to Cl 6 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 I, claim 2, or claim 3 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 thereof6. The paraffin suppressant composition of claim I, claim 2, or claim 3 wherein the paraffin suppressant comprises one or more ethoxylated nonylphenols, one or morenonyl phenol formaldehyde resists, dodecyl benzene sulfonic acid or a conjugate base thereof or any combination thereof7. 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 pamffin 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 Cl -Cl 2 alkanols, one or more linear, branched, or cyclic C5 to Cl 6 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 thereof9. The method of claim 7 wherein the nanoparticulate comprises carbon, silica, alumina, aluminosilicate, or any combination thereof.

10. The method of claim 7, claim 8, or claim 9 wherein the mixing is mixing the paraffin suppressant dispersion with a dry nanoparticulate.I i . The method of claim 7, claim 8, or claim 9 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 thereof12. The method of claim 10 wherein the mixing comprises sonicating..

13. The method of claim 11 wherein the mixing comprises sonicating.

14. 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 combinati on 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.

15. The treated petroleum oii of claim 14 wherein the nanoparticulate comprises silica, alumina, an aluminosilicate, carbon, or any combination thereof.

16. The treated petroleum oil of claim 14 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 thereof17. 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. The treated petroleum oil of claim 14, claim 15, claim 16, or claim 17 wherein the viscosity of the treated petroleum oil measured at a temperature between 60 °C and -4C'C is 5% to 50% less than the viscosi ty of a composition measured at the same temperature and comprising the crude oil and the paraffin inhibitor in the absence of the nanoparticulate.

19. A method of treating a petroleum oil, the method comprising mixing 0.01 ppm to 10,000 ppm by weigh t of a paraffin suppressant composition of claim 1 wit h a petroleum oil.

20. The method of claim 19, wherein the method further comprisesdispersing 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 Ci -Ci 2 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 morio-n-batyl ether, propylene glycol mono-methyl ether acetate, N,N- dimethyl acetamide, light aromatic naphtha, heavy aromatic naphtha, fuel oil, kerosene, diesel, or any combination thereof21 . The method of claim 19 or claim 20 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.22, Use of a nanoparticulate comprising carbon, silica, alumina, aluminosilicate, or any combination thereof to reduce the viscosity of a petroleum oil-paraffin inhibitor mixture.

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