Method for removing metals and solids from crude oil

Abstract

The present disclosure provides methods and compositions for removing metals, amines, and / or solids from a hydrocarbon medium. A composition of the present disclosure may include a lactam-containing polymer. A method of the present disclosure may include adding one or more lactam-containing polymers and / or salts thereof to a hydrocarbon medium and / or wash water; adding wash water to the hydrocarbon medium; mixing the hydrocarbon medium and the wash water to form an emulsion; and resolving the emulsion into an aqueous phase and a hydrocarbon phase having a reduced metals content.

Description

N12225USP1METHOD FOR REMOVING METALS AND SOLIDS FROM CRUDE OILTECHNICAL FIELD

[0001] The present disclosure relates to methods and compositions for removing metals, such as iron, and solids from a hydrocarbon medium, such as crude oil. More particularly, the disclosure relates to methods and compositions comprising lactam-containing polymers, and / or salts thereof, for removing metals and solids from hydrocarbon mediums in refinery desalting processes where the compositions are added to the medium and / or to the wash water.BACKGROUND

[0002] A few, but increasingly important, petroleum crude feedstocks contain levels of metals, such as iron and calcium, which render them difficult, if not impossible, to process using conventional refining techniques. Much of the solids encountered during crude oil desalting include iron, most commonly as particulate iron, such as iron oxide, iron sulfide, etc. Other metals that are desirably removed include, but are not necessarily limited to, calcium, zinc, vanadium, silicon, nickel, cobalt, copper, magnesium, manganese, and the like, and typically a number of these metals are present. Some of the metals may be present in a soluble form. The metals may be present in inorganic or organic forms. In addition to complicating the desalter operation, iron and other metals are of particular concern to further downstream processing, such as coking operations. Removing the metals from the crude oil early in the hydrocarbon processing stages is desired in order to eventually yield high quality coke while also limiting corrosion, fouling and processing problems.BRIEF SUMMARY

[0003] The present disclosure relates to methods and compositions for removing a metal, a solid, and / or an amine from a hydrocarbon medium.N12225USP1

[0004] In some embodiments, the disclosure provides a method of removing a metal from a hydrocarbon medium, comprising adding a composition to the hydrocarbon medium, wherein the composition comprises a lactam-containing polymer and / or a salt thereof, adding a wash water to the hydrocarbon medium, mixing the hydrocarbon medium and the wash water to form an emulsion, and resolving the emulsion into an aqueous phase and a hydrocarbon phase, wherein the hydrocarbon phase has a reduced metals content.

[0005] In some embodiments, a method of the present disclosure comprises (i) providing crude oil; (ii) adding a composition to the crude oil;(ii) adding a wash water to the crude oil; (iii) mixing the crude oil and the wash water to form an emulsion; and (iv) resolving the emulsion to provide an aqueous phase and crude oil phase having a reduced metal content, wherein the composition comprises a lactam-containing polymer and / or a salt thereof.

[0006] In certain embodiments, a composition of the present disclosure comprises a lactam-containing polymer and / or a salt thereof, and a hydrocarbon medium.

[0007] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the claims of this application.BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0008] A detailed description of the invention is hereafter described with specific reference being made to the drawings in which:

[0009] FIG. 1 shows % iron removal data from Example 1 ; and

[0010] FIG. 2 shows % iron removal data from Example 2.N12225USP1DETAILED DESCRIPTION

[0011] Various embodiments are described below. The relationship and functioning of the various elements of the embodiments will be better understood in light of the following detailed description. However, elements and embodiments are not strictly limited to those explicitly described below.

[0012] Examples of methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present disclosure. All publications, patent applications, patents and other reference materials mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control.

[0014] The term “polymer” as used herein includes not only polymers comprising a single monomer residue, but also polymers comprising more than one monomer residue. For example, a polymer as disclosed herein includes a copolymer, a terpolymer, a tetrapolymer, polymers comprising more than four different monomers, as well as polymers comprising, consisting of, or consisting essentially of two or more different monomer residues. Additionally, a “polymer” as disclosed herein may also include a homopolymer, which is a polymer comprising a single type of monomer unit.

[0015] Unless specified differently, the polymers of the present disclosure may be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, organic, inorganic, and / or functionally modified. A polymer of the present disclosure can be in the form of a solution, a dry powder, a liquid, or a dispersion, for example.

[0016] The present disclosure relates to compounds, compositions, and methods for removing a metal, a solid, and / or an amine from a hydrocarbonN12225USP1medium. In accordance with the present disclosure, the term “removing” encompasses completely removing the metal, amine, and / or solid from the hydrocarbon medium, removing a portion or the metal, amine, and / or solid form the hydrocarbon medium, or otherwise lowering an amount of the metal, amine, and / or solid in the hydrocarbon medium.

[0017] The compositions disclosed herein comprise one or more lactam-containing polymers. The lactam may comprise, for example, a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a sevenmembered ring, or any combination thereof.

[0018] Illustrative, non-limiting lactam-containing polymers may be selected from:homopolymer 5, 6, 7,>homopolymer 8,homopolymer 9, and any combination thereof, wherein n is an integer independently selected independently at each occurrence from about 2 to about 1 ,000. For example, each n may be independently selected from about 2 to about 800, about 2 to about 600, about 2 to about 400, about 2 to about 200, about 2 to about 100, about 2 to about 75, about 2 to about 50, about 2 to about 25, about 2 to about 10, about 10 to about 1,000, about 25 to about 1 ,000, about 50N12225USP1to about 1,000, about 75 to about 1 ,000, about 100 to about 1,000, about 200 to about 1 ,000, about 400 to about 1 ,000, about 600 to about 1 ,000, or about 800 to about 1,000.

[0019] Additional non-limiting examples of lactam-containing polymers include:copolymer 5,N12225USP1copolymer 6, and any combination thereof.

[0020] The x variable is an integer independently selected at each occurrence from about 2 to about 1 ,000. For example, each x may be independently selected from about 2 to about 800, about 2 to about 600, about 2 to about 400, about 2 to about 200, about 2 to about 100, about 2 to about 75, about 2 to about 50, about 2 to about 25, about 2 to about 10, about 10 to about 1 ,000, about 25 to about 1 ,000, about 50 to about 1 ,000, about 75 to about 1 ,000, about 100 to about 1 ,000, about 200 to about 1 ,000, about 400 to about 1 ,000, about 600 to about 1 ,000, or about 800 to about 1 ,000.

[0021] The y variable is an integer independently selected at each occurrence from about 2 to about 1 ,000. For example, each y may be independently selected from about 2 to about 800, about 2 to about 600, about 2 to about 400, about 2 to about 200, about 2 to about 100, about 2 to about 75, about 2 to about 50, about 2 to about 25, about 2 to about 10, about 10 to about 1 ,000, about 25 to about 1 ,000, about 50 to about 1 ,000, about 75 to about 1 ,000, about 100 to about 1 ,000, about 200 to about 1 ,000, about 400 to about 1 ,000, about 600 to about 1 ,000, or about 800 to about 1 ,000.

[0022] The z variable is an integer independently selected at each occurrence from about 2 to 1 ,000. For example, each z may be independently selected from about 2 to about 800, about 2 to about 600, about 2 to about 400, about 2 to about 200, about 2 to about 100, about 2 to about 75, about 2 to about 50, about 2 to about 25, about 2 to about 10, about 10 to about 1 ,000, about 25 to about 1 ,000, about 50 to about 1 ,000, about 75 to about 1 ,000, about 100 to about 1 ,000, about 200 to about 1 ,000, about 400 to about 1 ,000, about 600 to about 1 ,000, or about 800 to about 1 ,000.N12225USP1

[0023] Specific, non-limiting examples of lactam-containing polymers may be selected from poly(vinylpyrrolidone), poly(vinylpiperidone), poly (vinylcaprolactam), and a poly(vinylcaprolactam-co-vinylpyrrolidone) copolymer.

[0024] In some embodiments, the lactam-containing polymer may comprise one or more of the following commercially available polymers listed in Table 1.

[0025] Table 1 :

[0026] In Table 1 , AA = acrylic acid, VP = vinyl pyrrolidinone, VCP = vinyl caprolactam, PVP = poly(vinylpyrrolidone), and VIMA = N-methyl-N-vinylacetamide.

[0027] The lactam-containing polymer may be water-soluble and / or oilsoluble. In some embodiments, the lactam-containing polymer is a homopolymer.

[0028] A composition of the present disclosure may comprise any amount of the lactam-containing polymer. For example, a composition may comprise from about 1 wt. % to about 100 wt. % of the lactam-containing polymer, such as about 1 wt. % to about 90 wt. %, about 1 wt. % to about 80 wt. %, about 1 wt. % to about 70 wt. %, about 1 wt. % to about 60 wt. %, about 1 wt. % to about 50 wt.N12225USP1%, about 1 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, about 10 wt. % to about 95 wt. %, about 20 wt. % to about 95 wt. %, about 30 wt. % to about 95 wt. %, about 40 wt. % to about 95 wt. %, about 50 wt. % to about 95 wt. %, about 60 wt. % to about 95 wt. %, about 70 wt. % to about 95 wt. %, about 80 wt. % to about 95 wt. %, or about 90 wt. % to about 95 wt. %.

[0029] In addition to a lactam-containing polymer, a composition of the present disclosure may comprise (or exclude) an additional component.Illustrative, non-limiting examples of additional components include a solvent, a corrosion inhibitor, a salt dispersant, an oxyalkylate demulsifier, a scale inhibitor, a metal chelant, a wetting agent, an asphaltene dispersant, an antifoulant, an antifoam agent, an emulsion breaker, a pH modifier, or any combination thereof.

[0030] Illustrative examples of solvents include a polar solvent, a nonpolar solvent, or a combination thereof.

[0031] Non-limiting examples of solvents include any type of water (e.g., tap water, deionized water etc.), a brine, an alcohol (including straight chain or branched aliphatic, such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), an alkylene glycol (such as methylene glycol, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, etc.), a glycol ether (such as diethyleneglycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, etc.), a ketone (such as cyclohexanone, methyl ethyl ketone or diisobutylketone), an ether (such as diethyl ether), an alkylene carbonate (such as propylene carbonate), N-methylpyrrolidinone (NMP), N,N-dimethylformamide, a polyol (such as glycerin), kerosene, HAN (heavy aromatic naptha), naptha depleted HAN (NP-HAN), toluene, diethylene glycol monoethyl ether, xylene, a hydrocarbon, an amide, a nitrile, a sulfoxide, an ester, and any combination thereof.N12225USP1

[0032] In some embodiments, the corrosion inhibitor comprises an imidazoline. The imidazoline may be, for example, imidazoline derived from a diamine, such as ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetraamine (TETA), etc., and a long chain fatty acid, such as tall oil fatty acid (TOFA). Suitable corrosion inhibitors also include, but are not limited to, alkyl, hydroxyalkyl, alkylaryl, arylalkyl or arylamine quaternary salts, mono or polycyclic aromatic amine salts, imidazoline derivatives, mono-, di- or trialkyl or alkylaryl phosphate esters, phosphate esters of hydroxylamines, phosphate esters of polyols, an ester of alcoholamine, an alkoxylated amine and / or monomeric and / or oligomeric fatty acids, and / or any combination of the foregoing.

[0033] Illustrative, non-limiting examples of salt dispersants include calcium sulfonate, calcium phenate, choline chloride, and any combination thereof.

[0034] An illustrative example of an oxyalkylate demulsifier is a phenol-based polymer.

[0035] Illustrative examples of scale inhibitors include phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonic acids, polyacrylamides, salts of acrylamidomethyl propane sulfonate / acrylic acid copolymer (AMPS / AA), phosphinated maleic copolymer (PHOS / MA), salts of a polymaleic acid / acrylic acid / acrylamidomethyl propane sulfonate terpolymer (PMA / AA / AMPS), and any combination thereof.

[0036] Illustrative examples of metal chelants include ethylenediaminetetra acetic acid (EDTA), glycolic acid, malic acid, salt of gluconic acid, thioglycolic acid, tartaric acid, mandelic acid, citric acid, acetic acid, oxalic acid, nitrolotriacetic acid (NTA), ethylenediamine (EDA), methanesulfonic acid and any combination thereof.

[0037] An illustrative example of a wetting agent is a sulfonate polymer.

[0038] Illustrative examples of asphaltene dispersants and antifoulants include aliphatic sulfonic acids, alkyl aryl sulfonic acids, aryl sulfonates,N12225USP1lignosulfonates, alkylphenol / aldehyde resins and / or similar sulfonated resins, polyolefin esters, polyolefin imides, polyolefin esters with alkyl, alkylenephenyl or alkylenepyridyl functional groups, polyolefin amides, polyolefin amides with alkyl, alkylenephenyl or alkylenepyridyl functional groups, polyolefin imides with alkyl, alkylenephenyl or alkylenepyridyl functional groups, alkenyl / vinyl pyrrolidone copolymers, graft polymers of polyolefins with maleic anhydride or vinyl imidazole, hyperbranched polyester amides, polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkyl succinates, sorbitan monooleate, polyisobutylene succinic anhydride, and any combination thereof.

[0039] Illustrative examples of antifoam agents include polysiloxanes, glycols, and any combination thereof.

[0040] Illustrative examples of emulsion breakers include dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds, anionic, cationic and nonionic surfactants, resins, such as phenolic and epoxide resins, and any combination thereof.

[0041] Illustrative examples of pH modifiers include alkali hydroxides, alkali carbonates, alkali bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, and any combination thereof. For example, a pH modifier may include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium oxide, magnesium hydroxide, and any combination thereof. In some embodiments, a pH modifier may comprise a hydrophilic and / or amphiphilic amine, such as methyldiethanolamine (MDEA).

[0042] In certain embodiments, a composition and / or a lactam-containing polymer of the present disclosure comprises or excludes a functionalized polymer, an iodododecane group, a sulfonated polymer, a phosphonate, a phosphate, an amine, an imine, acrylic acid, and any combination thereof.N12225USP1

[0043] A composition of the present disclosure may comprise any amount of the additional component. For example, a composition may comprise from about 1 wt. % to about 100 wt. % of the additional component, such as about 1 wt. % to about 90 wt. %, about 1 wt. % to about 80 wt. %, about 1 wt. % to about 70 wt. %, about 1 wt. % to about 60 wt. %, about 1 wt. % to about 50 wt. %, about 1 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, about 10 wt. % to about 95 wt. %, about 20 wt. % to about 95 wt. %, about 30 wt. % to about 95 wt. %, about 40 wt. % to about 95 wt. %, about 50 wt. % to about 95 wt. %, about 60 wt. % to about 95 wt. %, about 70 wt. % to about 95 wt. %, about 80 wt. % to about 95 wt. %, or about 90 wt. % to about 95 wt. %.The compositions and / or compounds disclosed herein may be used in various methods for removing a metal, a solid, and / or an amine from a hydrocarbon medium.

[0044] A method may include, for example, removing a metal from a hydrocarbon medium. The method may comprise adding any composition disclosed herein to the hydrocarbon medium and / or to a wash water. A method may also comprise adding a wash water to the hydrocarbon medium and mixing the hydrocarbon medium and the wash water to form an emulsion. The emulsion may subsequently be resolved into an aqueous phase and a hydrocarbon phase, wherein the hydrocarbon phase has a reduced metal content.

[0045] In some embodiments, the composition may be added to the hydrocarbon medium before, after, and / or simultaneously with the wash water. In some embodiments, the composition may be added to the wash water before adding it to the hydrocarbon medium.

[0046] Methods of the present disclosure may also comprise adding one or more of the additional components disclosed herein to the hydrocarbon medium and / or wash water. In some embodiments, the additional component(s) may be added to the hydrocarbon medium before, after, and / or simultaneously with the lactam-containing polymer. In some embodiments, the additional componentN12225USP1may be added to the wash water before and / or after the wash water is added to the hydrocarbon medium.

[0047] The methods disclosed herein may also comprise or exclude adding a functionalized polymer, a polymer comprising an iodododecane group, a sulfonated polymer, a phosphonate, a phosphate, an amine, an imine, acrylic acid, or any combination thereof, to the hydrocarbon medium and / or the wash water.

[0048] The amount of additional component(s) added to the hydrocarbon medium and / or wash water is not particularly limited.

[0049] For example, the amount of the additional component(s) added to the hydrocarbon medium may be selected from about 1 ppm to about 5,000 ppm, such as from about 1 ppm to about 4,000 ppm, about 1 ppm to about 3,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1 ,000 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 200 ppm, about 1 ppm to about 100 ppm, or about 1 ppm to about 50 ppm.

[0050] The amount of additional component(s) added to the wash water may be selected from about 1 ppm to about 5,000 ppm, such as from about 1 ppm to about 4,000 ppm, about 1 ppm to about 3,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1,000 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 200 ppm, about 1 ppm to about 100 ppm, or about 1 ppm to about 50 ppm.

[0051] Similarly, the amount of lactam-containing polymer added to the wash water and / or hydrocarbon medium is not particularly limited.

[0052] For example, the amount of lactam-containing polymer added to the hydrocarbon medium may be selected from about 1 ppm to about 5,000 ppm, such as from about 1 ppm to about 4,000 ppm, about 1 ppm to about 3,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1 ,000 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 250N12225USP1ppm, about 1 ppm to about 200 ppm, about 1 ppm to about 100 ppm, or about 1 ppm to about 50 ppm.

[0053] Also, the amount of lactam-containing polymer added to the wash water may be selected from about 1 ppm to about 5,000 ppm, such as from about 1 ppm to about 4,000 ppm, about 1 ppm to about 3,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1 ,000 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 200 ppm, about 1 ppm to about 100 ppm, or about 1 ppm to about 50 ppm.

[0054] The location of the hydrocarbon medium is not particularly limited and the methods disclosed herein effectively remove metals, solids, and / or amines from hydrocarbon mediums in any location. In some embodiments, a desalter unit comprises the hydrocarbon medium. In such embodiments, a composition of the present disclosure may be added to the hydrocarbon medium before the hydrocarbon medium arrives at the desalter unit. If an industrial process comprises multiple desalter units, a composition of the present disclosure may be added to the medium before the medium arrives at any of the desalter units and / or a composition may be added between any of the desalter units.

[0055] The inventors unexpectedly discovered that addition of a lactam-containing polymer, either alone or with an additional component, to a hydrocarbon medium and / or to a wash water, in a hydrocarbon desalting operation, results in enhanced removal of unbound metal contaminants, such as iron, from the medium.

[0056] In a refinery crude oil desalting operation, a water-in-oil (w / o) emulsion is intentionally formed by adding water, commonly referred to as “wash water,” to the crude oil with the wash water being admitted on the order of about 3 to about 10 volume percent based on the crude oil. The wash water is added to the crude oil and mixed intimately to transfer impurities, such as chlorides, from the crude oil into the water phase. The w / o emulsion is then pumped into the desalter unitN12225USP1where separation of the phases occurs due to coalescence of the small water droplets into progressively larger droplets and eventual gravity separation of the oil and underlying water phase.

[0057] Desalters are ordinarily provided with electrodes to impart an electrical field in the desalter. This serves to polarize the dispersed water molecules. The so-formed dipole molecules exert an attractive force between oppositely charged poles with the increased attractive force increasing the speed of water droplet coalescence from about ten to about one hundred-fold. The water droplets also move quickly in the electrical field, thus promoting random collisions that further enhance coalescence.

[0058] Also, the desalters are generally provided with heat imparting means and pressure control means to respectively control temperature and pressure within the vessels. Typically, desalter temperatures are maintained at about 200 to about 300 °F. Heat lowers the viscosity of the continuous phase (e.g., crude oil) thereby speeding the settlement of the coalesced water droplets. It also increases the ability of bulk oil to dissolve certain organic emulsion stabilizers that may have been added or are naturally occurring in the crude oil.

[0059] Desalter pressure is kept high enough to prevent crude oil or water vaporization. Vaporization causes water carry over into the crude oil leaving the desalter. Desalter pressure at operating temperatures should generally be about 20 psi above the crude oil or water vapor pressure, whichever is lower.

[0060] Upon separation of the phases from the w / o emulsion, the crude oil is commonly drawn off the top of the desalter and sent to the fractionator tower in crude oil units or other refinery processes. The water phase containing water-soluble metal salt compounds and sediment is discharged as effluent.

[0061] With respect to refinery desalting processes, the present disclosure provides a method for removing a metal from crude oil including providing crude oil comprising the metal, adding any of the compositions disclosed herein to the crude oil, adding wash water to the crude oil, mixing the crude oil and the washN12225USP1water to form an emulsion, and resolving the emulsion to provide an aqueous phase and a crude oil phase, where the resulting crude oil phase has a reduced metal content.

[0062] The composition may be added to the crude oil before the wash water is added to the crude oil, the composition may be added to the crude oil after the wash water is added to the crude oil, and / or the composition may be added to the crude oil with the wash water. In some embodiments, the composition may be added to the wash water.

[0063] Any of the presently disclosed additional components may be added to the crude oil and / or wash water before, after, and / or with the lactam-containing polymer. In some embodiments, the method further comprises adding a functionalized polymer, a polymer comprising an iodododecane group, a sulfonated polymer, a phosphonate, a phosphate, an amine, an imine, acrylic acid, or any combination thereof, to the crude oil and / or to the wash water.

[0064] In illustrative embodiments, the method further comprises removing a solid and / or an amine from the crude oil, wherein the solid is selected from dirt, clay, silt, an asphaltene, sand, a metal, and any combination thereof.

[0065] Metals suitable for removal using the process of the present disclosure include, but are not limited to, iron, calcium, zinc, vanadium, silicon, nickel, cobalt, copper, magnesium, manganese, sodium, potassium, and the like, and any combination thereof. For example, the metal may include iron and / or calcium. In illustrative embodiments, the metal, such as iron, may be in a bound form and / or an unbound form.

[0066] Any aqueous medium may be used as wash water in accordance with the processes disclosed herein. For example, the wash water may comprise well water, cooling water, stripped sour water, overhead water (i.e., at atmospheric or vacuum distillation tower), fresh water or fire water, municipal water, recycled wash water (i.e., recirculation of wash water for two-stage desalter) and any combination thereof.N12225USP1

[0067] In illustrative, non-limiting embodiments, a hydrocarbon medium may comprise crude oil, atmospheric residua, vacuum residua, a deasphalted oil, liquified coal, slop oil, a refinery feedstock, pyrolysis oil, biocrude, and any combination thereof.

[0068] The hydrocarbon medium may also comprise, for example, an acid and / or ammonia.

[0069] In some embodiments, the hydrocarbon medium may further comprise produced water, fresh water, seawater, recycled water, salt water, surface water, carbon dioxide, hydrogen, or any mixture thereof. In certain embodiments, the hydrocarbon medium comprises a liquid hydrocarbon, such as crude oil, heavy oil, processed residual oil, bituminous oil, a coker oil, a coker gas oil, a fluid catalytic cracker feed, a gas oil, naphtha, a fluid catalytic cracking slurry, and any combination thereof.

[0070] A medium treated with a composition and / or compound of the present disclosure can be at any selected temperature, such as ambient temperature or an elevated temperature. For example, the medium (e.g., crude oil) may be at a temperature of from about 0 °C to about 250 °C. In some embodiments, the medium may be at a temperature of from about 50 °C to about 150 °C, about 70 °C to about 140 °C, about 80 °C to about 135 °C, about 85 °C to about 130 °C, or about 90 °C to about 125 °C.

[0071] The foregoing may be better understood by reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the present disclosure.

[0072] EXAMPLES

[0073] A crude oil sample and water were added to a 40-mL vial equipped with a pressure release valve. A demulsifier (ethoxylated nonylphenol formaldehyde resin) and one or more lactam-containing polymer(s) were then added to each vial. One vial, the control, contained no lactam-containing polymer. The vial contents were then mixed thoroughly with a Turrax™N12225USP1homogenizer at 10,000 rpm for 30 seconds. The resulting vial was placed on a heating block at about 80 °C for about 1 hour, and then allowed to cool to about 20 °C. Once cooled, a sample of oil was removed from the upper phase in the vial and analyzed by Petra Max XRF for Iron (30s ASTM D4294 Sulfur calibration).

[0074] In a first example, the following test conditions were used:- Iron concentration in crude oil: 44.69 ppm- Test temperature: 80 °C- Crude Oil: 27 mL- Wash Water: 3 mL- Lactam-containing polymer dosage: about 50 ppm- Demulsifier dosage: about 10 ppm

[0075] In a second example, the following test conditions were used:- Iron concentration in crude oil: 37.77 ppm- Test temperature: 80 °C- Crude Oil: 13.5 mL- Wash Water: 1.5 mL- Lactam-containing polymer dosage: about 50 ppm- Demulsifier dosage: about 10 ppm

[0076] The results of the first and second examples, which are shown in FIG.1 and FIG. 2, respectively, indicate that the methods and compositions of the present disclosure can effectively remove about 60-70% of the iron from crude oil.

[0077] Without wishing to be bound by theory, it is believed that the lactam-containing polymers disclosed herein may form composite hydrogels of different sizes (e.g., macrogels, microgels and nanogels) with inorganic and / or metallic inclusions, which makes the lactam-containing polymers effective metal, solid, and / or amine removing agents.

[0078] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While this invention may be embodied in many different forms, thereN12225USP1are described in detail herein specific examples of embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. In addition, unless expressly stated to the contrary, use of the term “a” is intended to include “at least one” or “one or more.” For example, “a lactam-containing polymer” is intended to include “at least one lactam-containing polymer” or “one or more lactam-containing polymers.”

[0079] Any ranges given either in absolute terms or in approximate terms are intended to encompass both, and any definitions used herein are intended to be clarifying and not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges (including all fractional and whole values) subsumed therein.

[0080] Any composition disclosed herein may comprise, consist of, or consist essentially of any compound, element, component and / or ingredient disclosed herein or any combination of two or more of the compounds, elements, components or ingredients disclosed herein.

[0081] Any method disclosed herein may comprise, consist of, or consist essentially of any method step disclosed herein or any combination of two or more of the method steps disclosed herein.

[0082] The transitional phrase “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements, components, ingredients and / or method steps.N12225USP1

[0083] The transitional phrase “consisting of” excludes any element, component, ingredient, and / or method step not specified in the claim.

[0084] The transitional phrase “consisting essentially of” limits the scope of a claim to the specified elements, components, ingredients and / or steps, as well as those that do not materially affect the basic and novel characteristic(s) of the claimed invention.

[0085] Unless specified otherwise, all molecular weights referred to herein are weight average molecular weights and all viscosities were measured at 25 °C with neat (not diluted) polymers.

[0086] As used herein, the term "about" refers to the cited value being within the errors arising from the standard deviation found in their respective testing measurements, and if those errors cannot be determined, then "about" may refer to, for example, within 5%, 4%, 3%, 2%, or 1% of the cited value.

[0087] Furthermore, the invention encompasses any and all possible combinations of some or all of the various embodiments described herein. It should also be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. It is therefore intended that such changes and modifications be covered by the appended claims.

Claims

N12225USP1CLAIMSWhat is claimed is:

1. A method of removing a metal from a hydrocarbon medium, comprising:adding a composition to the hydrocarbon medium, wherein the composition comprises a lactam-containing polymer and / or a salt thereof,adding a wash water to the hydrocarbon medium,mixing the hydrocarbon medium and the wash water to form an emulsion, andresolving the emulsion into an aqueous phase and a hydrocarbon phase, wherein the hydrocarbon phase has a reduced metal content.

2. The method of claim 1, further comprising adding the composition to the hydrocarbon medium before, after, and / or simultaneously with the wash water.

3. The method of claim 1 or claim 2, wherein the polymer is a homopolymer.

4. The method of any one of the preceding claims, wherein the lactam comprises a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or any combination thereof.

5. The method of any one of the preceding claims, wherein the lactam-containing polymer is selected from the group consisting ofN12225USP1, and any combination thereof, wherein n is an integer independently selected at each occurrence from about 2 to about 1,000.

6. The method of any one of claims 1 to 4, wherein the lactam-containing polymer is selected from the group consisting ofN12225USP1any combination thereof, wherein x is an integer independently selected at each occurrence from about 2 to about 1 ,000, y is an integer independently selected at each occurrence from about 2 to about I ,000, and z is an integer independently selected at each occurrence from about 2 to about 1 ,000.

7. The method of any one of the preceding claims, wherein the lactam-containing polymer is water-soluble and / or oil-soluble.

8. The method of any one of the preceding claims, wherein a desalter unit comprises the hydrocarbon medium.

9. The method of any one of claims 1 to 7, further comprising adding the composition to the hydrocarbon medium before the hydrocarbon medium arrives at any desalter units.

10. The method of any one of the preceding claims, wherein the metal is selected from the group consisting of iron, calcium, zinc, vanadium, silicon, nickel, cobalt, copper, magnesium, manganese, and any combination thereof.I I . The method of any one of the preceding claims, wherein the hydrocarbon medium is selected from the group consisting of crude oil, atmospheric residua, vacuum residua, a deasphalted oil, liquified coal, slop oil, a refinery feedstock, pyrolysis oil, biocrude and any combination thereof.N12225USP112. The method of any one of the preceding claims, wherein the hydrocarbon medium comprises an acid and / or ammonia.

13. The method of any one of the preceding claims, further comprising adding an additional component to the hydrocarbon medium and / or wash water, wherein the additional component is selected from the group consisting of water, a solvent, a corrosion inhibitor, a salt dispersant, an oxyalkylate demulsifier, a scale inhibitor, a metal chelant, a wetting agent, an asphaltene dispersant, an antifoulant, an antifoam agent, and any combination thereof.

14. The method of claim 13, further comprising adding the additional component to the hydrocarbon medium before, after, and / or simultaneously with the lactam-containing polymer.

15. The method of claim 13, further comprising adding the additional component to the wash water before and / or after the wash water is added to the hydrocarbon medium.

16. The method of any one of claims 13 to 15, further comprising adding from about 1 ppm to about 5,000 ppm of the additional component to the hydrocarbon medium and / or wash water.

17. The method of any one of the preceding claims, wherein the lactam-containing polymer and / or the salt thereof excludes a functionalized polymer, an iodododecane group, a sulfonated polymer, a phosphonate, a phosphate, an amine, an imine, acrylic acid, and any combination thereof.

18. The method of any one of the preceding claims, wherein the method excludes adding a functionalized polymer, a polymer comprising an iodododecaneN12225USP1group, a sulfonated polymer, a phosphonate, a phosphate, an amine, an imine, acrylic acid, or any combination thereof, to the hydrocarbon medium and / or the wash water.

19. The method of any one of the preceding claims, further comprising removing a solid and / or an amine from the hydrocarbon medium.

20. The method of any one of the preceding claims, further comprising adding from about 1 ppm to about 5,000 ppm of the lactam-containing polymer to the hydrocarbon medium.

21. The method of any one of the preceding claims, further comprising adding from about 1 ppm to about 5,000 ppm of the lactam-containing polymer to the wash water.

22. A refinery desalting method for removing a metal from crude oil, comprising: (i) providing crude oil;(ii) adding a composition to the crude oil;(ii) adding a wash water to the crude oil;(iii) mixing the crude oil and the wash water to form an emulsion; and(iv) resolving the emulsion to provide an aqueous phase and a crude oil phase having a reduced metal content, wherein the composition comprises a lactam-containing polymer and / or a salt thereof.

23. The method of claim 22, further comprising adding the composition to the crude oil upstream of the wash water.

24. The method of claim 22 or claim 23, further comprising adding the composition to the wash water.N12225USP125. The method of any one of claims 22 to 24, further comprising adding from about 1 ppm to about 5,000 ppm of the lactam-containing polymer and / or the salt thereof to the crude oil.

26. A composition, comprising:a lactam-containing polymer and / or a salt thereof, anda hydrocarbon medium.

27. The composition of claim 26, wherein the hydrocarbon medium comprises crude oil.

28. The composition of claim 26 or claim 27, wherein the hydrocarbon medium comprises a metal, a solid, and / or an amine.

29. The composition of any one of the preceding claims, wherein the lactam-containing polymer comprises a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or any combination thereof.

30. The composition of any one of the preceding claims, wherein the lactam-containing polymer is selected from the group consisting of, and any combination thereof, wherein n is an integer independently selected at each occurrence from 2 to 1000.N12225USP131. The composition of any one of the preceding claims, wherein the lactam-containing polymer is selected from the group consisting ofof, wherein x is an integer independently selected at each occurrence from 2 to 1000, y is an integerN12225USP1independently selected at each occurrence from 2 to 1000, and z is an integer independently selected at each occurrence from 2 to 1000.

32. The composition of any one of the preceding claims, wherein the lactam-containing polymer and / or the salt thereof excludes a functionalized polymer, an iodododecane group, a sulfonated polymer, a phosphonate, a phosphate, an amine, an imine, acrylic acid, and any combination thereof.

Images