EA041390B1 - DOWNHOLE ASPHALTENES INHIBITORS BASED ON IONIC LIQUID AND METHODS OF THEIR APPLICATION - Google Patents

Description

Technical field

The present disclosure relates to an asphaltene inhibitor composition, a method for treating petroleum hydrocarbon fluid with said composition, and a method for inhibiting or preventing the formation or precipitation of asphaltenes during production and recovery of petroleum hydrocarbon fluids from oil reservoirs.

Prerequisites for the creation of the invention

Crude oil is a complex mixture containing many different hydrocarbons, varying in appearance and ranging in consistency from water to tarry solids. The high viscosity of the heavy crude oil is at least partly due to the presence of asphaltenes. Additionally, asphaltenes are known to adversely affect the viscoelasticity and fluidity of crude oils.

Asphaltene deposits are known to flocculate during oil production operations and form deposits at various locations. In oil-bearing underground formations, oil recovery is difficult due to the presence of agglomerates of such deposits in the pores of the formation. It is known that such deposits also coat wellbores. In some cases, asphaltene deposits block production lines and pipes by hardening on the surface of the downhole equipment. Sometimes the presence of asphaltene deposits leads to a slowdown or complete cessation of production. In addition, it is known that such deposits significantly reduce the productive period of the well.

In addition to operational problems, asphaltene deposits are known to cause safety problems in the extraction and processing of hydrocarbons. In some cases, for example, asphaltenes cause critical safety valves to fail.

The negative effects of asphaltene precipitation are even more pronounced during oil refining. For example, the presence of asphaltenes is known to lead to poisoning of catalysts, formation of coke and fouling of heat exchangers.

In recent years, considerable effort has been focused on the development of treatments that adequately address the problems caused by asphaltene deposits. Such treatment agents include agents that inhibit, prevent or reduce the deposition and/or accumulation of asphaltenes. Asphaltenes are very complex heterocyclic macromolecules. While some treatments have been successful in inhibiting the deposition of some asphaltenes, in many cases their success has been severely limited. Thus, improved compositions are required to inhibit the deposition and/or accumulation of asphaltenes.

Disclosure of the essence of the invention

In one embodiment, the present invention relates to a method for improving the effectiveness of an asphaltene inhibitor in the production, storage, transportation, or processing of a petroleum hydrocarbon fluid. According to this method, the asphaltene inhibitor is brought into contact with the ionic liquid during a production or processing operation, or before or during storage or transportation of petroleum hydrocarbon fluid. An ionic liquid has a cation R1R ² R ³ R ⁴ N ⁺ or R'RjJN+ijN+RjR'R ⁷ and an anion where R ¹ , R ² , R ³ , R , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen , a straight or branched C1.30 alkyl group, benzyl, a C7_30 alkylbenzyl group, a C7.30 arylalkyl group, a straight or branched C330 alkenyl group, a C1.30 hydroxyalkyl group, a C7.30 hydroxyαkylbenzyl group, an oxyalkylene or polyoxyalkylene group, or a zwitterion; R ⁸ is straight or branched C1. ₃₀ alkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

In another embodiment, the present invention relates to an asphaltene inhibitor composition that contains an ionic liquid and an asphaltene inhibitor. An ionic liquid has a cation κΆκέΆ or R1R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen , a straight or branched C1.30 alkyl group, benzyl, a C7.30 alkylbenzyl group, a C7.30 arylalkyl group, a straight or branched C3.30 alkenyl group, a C1.30 hydroxyalkyl group, a C7.30 hydroxyalkylbenzyl group, an oxyalkylene or polyoxyalkylene group, or a zwitterion; R ⁸ is straight or branched C1. ₃₀ αkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

In another embodiment, the invention provides a petroleum hydrocarbon fluid that contains the asphaltene inhibitor composition described in the above paragraphs.

In another embodiment, a method is provided for improving the productivity of producing a petroleum hydrocarbon fluid from a subterranean formation. In this embodiment, the asphaltene inhibitor composition described in the above paragraphs is injected into the well. The asphaltene inhibitor composition inhibits, reduces or prevents the formation, agglomeration and/or accumulation of asphaltenes in the produced fluid. The asphaltene inhibitor composition is capable of further preventing or reducing the precipitation of asphaltenes from a petroleum hydrocarbon fluid.

In another embodiment, the invention provides a method for inhibiting, reducing or preventing the formation, agglomeration and/or accumulation of asphaltene deposits in an underground oil reservoir, pipeline, column or refinery. In this embodiment, a petroleum hydrocarbon fluid in a subterranean reservoir, pipeline, column, or refinery is contacted with the asphaltene inhibitor composition described in the above paragraphs. Contacting the fluid with the asphaltene inhibitor composition in the oil reservoir, pipeline, column, or refinery may further inhibit, prevent, or reduce the precipitation of asphaltenes from the fluid.

In another embodiment, a method for improving the stability of a petroleum hydrocarbon fluid is provided, wherein the hydrocarbon fluid is contacted with an asphaltene inhibitor composition as described in the above paragraphs.

In another embodiment, a method is provided for treating a petroleum hydrocarbon fluid, wherein the fluid is brought into contact with a phenolic resin and an ionic liquid. An ionic liquid has a cation R1R ² R ³ R ⁴ N ⁺ or R'R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen, a straight or branched Aralkyl group, benzyl, an Aralkylbenzyl group, a C7.30 arylalkyl group, a straight or branched C3.30 alkenyl group, a C1.30 hydroxyalkyl group, a C7.30 hydroxyalkylbenzyl group, an oxyalkylene or polyoxyalkylene group, or alternatively zwitterion; R ⁸ is straight or branched C1. ₃₀ αkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

In another embodiment, an asphaltene inhibitor composition is provided that contains a phenol-aldehyde resin and an ionic liquid containing the cation R1R ² R ³ R ⁴ N ⁺ or κΆΓΝ+ύΝ+ΑΓΑ and an anion, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen, straight or branched Aralkyl group, benzyl, Aralkylbenzyl group, Ararylalkyl group, straight or branched C ₃ . ₃₀ an alkenyl group, an Arhydroxyalkyl group, an Arhydroxyalkylbenzyl group, an oxyalkylene or polyoxyalkylene group, or a zwitterion; R ⁸ is straight or branched Aralkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

Brief description of graphic materials

The following figures, which are part of the present description, are included to demonstrate some aspects of various embodiments of the present invention and are referred to in the detailed description in this document. In the description with reference to the accompanying drawings, like elements are given the same numbering.

In FIG. 1 shows the results of an Asphaltene Centrifuge Stability Analytical (ACSAA) test at 25° C. for crude oil No. 1 treated with phenolic resin asphaltene inhibitor No. 1 alone or in combination with a polyamine additive or various ionic liquid synergists.

In FIG. 2 shows test results as ACSAA at 25° C. for crude oil #1 treated with phenolic resin asphaltene inhibitor #2 alone or in combination with an amine, a polyamine additive, or two ionic liquid synergists.

In FIG. 3 shows the results of an ACSAA test at 25° C. for crude oil #2 treated with phenolic resin asphaltene inhibitor #3 alone or in combination with an amine or several ionic liquid synergists.

In FIG. 4 shows test results as ACSAA at 25° C. for crude oil #3 treated with phenolic resin asphaltene inhibitor #3 alone or in combination with an amine or several ionic liquid synergists.

In FIG. Figure 5 shows test results as ACSAA at 25, 60, and pseudo 80°C for crude oil #4 treated with phenolic resin asphaltene inhibitors #2 and #4 alone or in combination with an amine or ditallow dimethylammonium hydroxide ionic liquid synergist. .

In FIG. 6 shows test results as ACSAA at 25, 60 and pseudo 80°C for crude oil #4 treated with phenolic resin asphaltene inhibitor #2 alone or in combination with various ionic liquid synergists.

In FIG. 7 shows test results as ACSAA at 25, 60, and pseudo 80°C for crude oil #4 treated with phenolic resin asphaltene inhibitor #2 alone or in combination with amine or various ionic liquid synergists.

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Detailed Description of the Preferred Embodiments

The characteristics and advantages of the present invention, as well as additional features and beneficial effects, will become apparent to those skilled in the art upon reading the following detailed description of the exemplary embodiments. The description contains specific details, such as types of materials, compositions, and processing conditions, to provide a complete description of the embodiments of the invention. Only those steps of the method, formula and structure that are necessary for understanding the embodiments of the invention are described in detail below.

It should be understood that the description provided herein, which provides exemplary embodiments, is not intended to limit the claims of this patent. On the contrary, the aim is to cover all modifications, equivalents and alternatives that fall within the scope of the claims.

In this document and in the appended claims, certain terms are used to refer to specific components. One of skill in the art will appreciate that different people may refer to a component in different ways. This document does not intend to distinguish between components that differ in name but not in function. In addition, the terms including and containing are used herein and in the appended claims in a non-limiting manner and, thus, they should be interpreted as meaning including, without limitation..... In addition, reference in this document and in the appended claims components and aspects in the singular does not limit the present description or the appended claims to only one such component or aspect, but should be interpreted generally as one or more, depending on what is appropriate and desirable in each particular case.

All ranges described herein include endpoints, and endpoints can be independently combined with each other. This document assumes that a term with a plural ending in brackets (e.g. (s)) includes both the singular and the plural of the term it modifies, thus including at least one such term (e.g., the term dispersive( e) the agent(s) includes at least one dispersing agent). The term optional or optional means that the parameter described below may or may not be present, and that this description includes the cases in which the parameter occurs and the cases in which it is not used. As used herein, the term combination includes components, compounds, mixtures, complexes, reaction products, and the like. All reference documents are incorporated herein by reference.

The use of singular and plural forms and similar references in the context of the description of the present invention (in particular, in the context of the following claims) should be understood as covering both the singular and the plural, unless otherwise indicated herein or unless it is clearly contradicted context.

As used herein, the term petroleum hydrocarbon fluid includes crude oil, shale oil, shale gas condensate, bitumen, diluted bitumen (dil-bit), petroleum refinery fractions, including distillates, including coking distillates, alkylates, finished fuels, including diesel fuel, light fuel and biofuels, finished petroleum products, reformates, cycle oil, residual oil, fuel gas, flare gas, propane, butane, liquefied petroleum gas (LPG), natural gas condensate, natural gas liquid (NGL) and combinations thereof . The asphaltene inhibitor compositions described herein are particularly suitable for crude oil, bitumen, diesel fuel, light fuel oil, biofuels, residual oil, fuel gas, flare gas, propane, butane, liquefied petroleum gas (LPG), natural gas liquid ( NGL), refined petroleum fractions (including gas oils and light lubricating oils), and combinations thereof. In addition, any of the above may contain water, aqueous salt solutions, gases such as hydrocarbon gases, or a combination thereof.

As used herein, the term asphaltene inhibitor includes a treatment agent capable of inhibiting, preventing or reducing the formation, agglomeration and/or accumulation of asphaltene deposits, as well as a treatment agent capable of inhibiting, preventing or reducing asphaltene deposition.

As used herein, the term asphaltene inhibitor composition refers to a product resulting from contacting an asphaltene inhibitor with an ionic liquid. This term includes compounds, mixtures, complexes and reaction products of an ionic liquid and an asphaltene inhibitor.

As used herein, the term conduit refers to any conduit, pipe, tubular, flow conduit, conveyance line, or other conduit through which a chemical is transported or contacted, including a petroleum hydrocarbon fluid. The term column includes any equipment or container with which the petroleum hydrocarbon fluid is in contact, such as heat exchangers, etc. A pipeline or string section includes, without limitation, reservoirs, wells, pipelines and transportation lines leading to or from an underground oil reservoir (including wells), refineries, fluid handling facilities, storage containers, and shipping containers. containers.

The addition of certain ionic liquids to conventional asphaltene inhibitors improves asphaltene stabilization and inhibition compared to using the conventional asphaltene inhibitor alone. This improvement is noted in production fluids extracted from the reservoir, treated fluids, fluids stored in columns, as well as transported fluids. When a petroleum hydrocarbon fluid is treated with an ionic liquid/asphaltene inhibitor mixture, less asphaltene deposits are formed in the production, processing, storage, or pumping of the petroleum hydrocarbon fluid than when the asphaltene inhibitor itself is used. When a petroleum hydrocarbon fluid is treated with an ionic liquid/asphaltene inhibitor mixture, less agglomerates or accumulations of asphaltene deposits are formed in the production, processing, storage, or pumping of the petroleum hydrocarbon fluid than when the asphaltene inhibitor alone is used. When a petroleum hydrocarbon fluid is treated with an ionic liquid/asphalten inhibitor mixture during production, processing, storage, or pumping of the petroleum hydrocarbon fluid, less asphaltenes are deposited from the petroleum hydrocarbon fluid than when the asphaltene inhibitor itself is used.

These results are very surprising since ionic liquids do not show an increase in the stability of asphaltenes. This allows for more efficient and effective management of the deposition, accumulation and/or agglomeration of asphaltenes during the extraction, storage, transportation and processing of crude oil.

For example, phenolic resins are often used as asphaltene stabilizers and inhibitors to reduce deposition and address asphaltene-related fluid handling problems. Phenolic resins are often used with amine or polyamine additives. Although ionic liquids by themselves do not improve the stability of asphaltenes, the use of ionic liquids in combination with phenolic resins (with or without amine or polyamine additives) inhibits or reduces the deposition, agglomeration of asphaltenes, as well as the accumulation of their deposits, and significantly increases stability of asphaltenes in petroleum hydrocarbon fluids. Deposition of asphaltenes from petroleum hydrocarbon fluids is also noted.

In a preferred embodiment, the ionic liquids are used to improve the effectiveness of an asphaltene inhibitor in the production of petroleum hydrocarbon fluids, the processing of petroleum hydrocarbon fluids (including processing in a refinery), the storage of petroleum hydrocarbon fluid, and the pumping of petroleum hydrocarbon fluid. Contacting the ionic liquid with an asphaltene inhibitor effectively inhibits, reduces, prevents, and/or controls asphaltene deposition, accumulation, and/or agglomeration in produced fluids, processed fluids, stored fluids, and transport fluids as well.

The asphaltene inhibitor composition stabilizes the oil fluid during its production, processing, storage and transportation, minimizing the formation or precipitation of asphaltenes. In addition, the asphaltene inhibitor composition minimizes the precipitation of asphaltenes.

In a preferred embodiment, the asphaltene inhibitor composition may be introduced into the oil reservoir during a well treatment operation. In addition, to reduce, inhibit or prevent the deposition, agglomeration or accumulation of asphaltene deposits in produced fluids, this composition minimizes the formation and deposition of deposits and agglomerates on the surfaces of flow pipelines and columns, as well as in the wellbore during crude oil production.

Typically, the composition is introduced into an oil reservoir during a drilling, pumping, or stimulation operation (including hydraulic fracturing, acidizing, etc.). In one embodiment, the asphaltene inhibitor composition may be prepared elsewhere or during processing and then injected into an oil reservoir. In an alternative embodiment, the asphaltene inhibitor and the ionic liquid may be pumped into the oil reservoir at the same time or during separate pumping steps.

Any known method for introducing the asphaltene inhibitor composition into an oil reservoir may be used. For example, a pressurization process can be used to deliver an asphaltene inhibitor composition to an oil reservoir. In another embodiment, the asphaltene inhibitor composition may be applied during a continuous or batch injection process through a capillary line, down the annulus backside, through a hose line, or through a combination of a hose line and a capillary line.

In addition to contacting the asphaltene inhibitor in the oil reservoir, the ionic liquid may be contacted with the asphaltene inhibitor during processing of the petroleum hydrocarbon fluid, during transportation or storage of the petroleum hydrocarbon fluid, or at any time in between. In such cases, the ionic liquid and the asphaltene inhibitor may be introduced into the oil fluid in a storage tank, a pumping column, a pipeline or column, a treatment unit, a refinery stream, etc., as well as in separate streams. In an alternative embodiment, the asphaltene inhibitor composition may be first formulated and then administered. Contacting the ionic liquid and the asphaltene inhibitor (whether administered as separate streams or as an asphaltene inhibitor composition) results in the inhibition, prevention, or reduction of deposition, agglomeration, or accumulation of asphaltene deposits on the surface of the pipeline, column, or vessel. The piping or tank is usually made of metal, while the column is usually made of metal, plastic or glass.

The contacting of the ionic liquid and the asphaltene inhibitor can be carried out at a temperature of from about -50°C to about 250°C, for example from about -5°C to about 200°C or from about 20°C to about 150°C, and at an absolute pressure of about 14.7 psig (psi abs.) to about 40,000 psig abs. or from about 14.7 psi abs. up to about 20,000 psi abs.

If the asphaltene inhibitor composition is present during production, processing, storage and pumping, the stability of the petroleum hydrocarbon fluid is significantly improved. A petroleum hydrocarbon fluid containing an asphaltene inhibitor composition is more stable than a similar fluid that differs only in the absence of an ionic liquid. Contacting the fluid with the ionic liquid and the asphaltene inhibitor provides better stabilization of the petroleum hydrocarbon fluid by reducing the deposition/accumulation of asphaltenes (in terms of amount, trend and/or rate of deposition/accumulation). Thus, the production, processing, storage, and pumping of petroleum hydrocarbon fluids are improved by the asphaltene-inhibiting composition described herein.

The synergy provided by the asphaltene-inhibiting composition can be noted based on the amount of asphaltenes deposited when using the asphaltene inhibitor itself as compared to using the asphaltene-inhibiting composition described herein instead. In addition, the effectiveness of the combination of ionic liquid and asphaltene inhibitor is significantly increased compared to the effectiveness of each of the components used separately. In one non-limiting example, the activity or effectiveness of an asphaltene inhibitor is increased by at least 25% and sometimes by 50% or more when used in combination with an ionic liquid. An example of synergy is that when using a combination of an ionic liquid and an asphaltene inhibitor, the overall effectiveness of inhibiting or preventing the formation of deposits or agglomerates of asphaltenes is increased compared to using each of the components alone.

Typically, the weight ratio of asphaltene inhibitor to ionic liquid in the asphaltene composition is from about 5:95 to about 3:1.

In some cases, the asphaltene inhibitor and the ionic liquid are a compound, and this compound is characterized by the indicated synergy. In other cases, synergism is determined by the formation of a complex between the ionic liquid and the asphaltene inhibitor.

In other cases, bringing the ionic liquid into contact with the asphaltene inhibitor and the ionic liquid results in the formation of a reaction product. The synergy of the asphaltene inhibitor and the ionic liquid in the reaction product is determined by its increased efficiency compared to the case of using the ionic liquid or the asphaltene inhibitor alone. In some cases, the amount of asphaltene inhibitor in the reaction product may be from about 3 to about 99 wt.%.

The ionic liquids used herein have a cation R1R ² R ³ R ⁴ N ⁺ or R1R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen, straight or branched C1.30 alkyl group, benzyl, C7.30 alkylbenzyl group, C7.30 arylalkyl group, straight or branched C3.30α alkenyl group, C1.30 hydroxyalkyl group, C7.30 hydroxyalkylbenzyl group, an oxyalkylene or polyoxyalkylene group or a zwitterion (for example, obtained by oxyalkylation of an amine with an alkylene oxide); R ⁸ is straight or branched C1. ₃₀ alkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

For basic anions, alkyl carbonates may have the formula ROCO2 ^- where R is a halogenated or non-halogenated linear or branched alkyl or hydroxyalkyl group, preferably a halogenated or non-halogenated linear or branched Ci. ₈ or ^^ alkyl group. Examples of alkyl carbonates may be selected from methyl, ethyl, propyl, butyl, 2-ethylhexyl, octyl, ethylene and propylene carbonates.

Examples of carboxylates include formate, acetate, propionate, octanoate, laurate, benzoate, nbutyrate, isobutitrate, pivalate, as well as C ₁₈ fatty acids such as oleate, linoleate and stearate. Examples of hydroxycarboxylates include glycolate, lactate, citrate, glucarate and gluconate.

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Alkoxides have the formula RO- where R is _C1-18 alkyl, Cb. ₁₂ aryl or C ₅ - ₁₂ cycloalkyl. Examples of alkoxides are t-butoxide, n-butoxide, isopropoxide, npropoxide, isobutoxide, ethoxide, methoxide, n-pentoxide, isopentoxide, 2-ethylhexoxide, 2-propylheptoxide, nonoxide, octoxide, decoxide, and their isomers. Preferably the alkoxides are t-butoxide, isopropoxide, ethoxide or methoxide. As a rule, tert-butoxide and methoxide are indicated. The alkoxides may further be homopolymers, copolymers or terpolymers of ethylene or propylene oxide (which may optionally be cross-linked). Suitable cross-linking agents include bisphenol A or maleic anhydride.

In specific embodiments, the basic anions include hydroxide, bicarbonate, methyl carbonate, tert-butoxide, methoxide, or a combination thereof. As a rule, hydroxide is indicated.

As used herein, the term alkyl refers to a straight chain or branched saturated monovalent hydrocarbon group, whether straight or branched chain is specifically indicated; aryl refers to an aromatic monovalent group containing only carbon in the aromatic ring or rings; arylalkyl refers to an alkyl group that has been substituted with an aryl group, benzyl being an example of an arylalkyl group; alkylbenzyl refers to a benzyl group that has been substituted with an alkyl group on an aromatic ring; hydroxyalkyl refers to an alkyl group that has been substituted with a hydroxyl group, with 2-hydroxyethyl being an example of a hydroxyalkyl group; hydroxyalkylbenzyl refers to a benzyl group that has been substituted with a hydroxyalkyl group as defined herein on an aromatic ring; alkylene refers to a straight or branched saturated divalent hydrocarbon group, and alkenyl refers to a straight or branched monovalent hydrocarbon group having at least two carbon atoms linked by a carbon-carbon double bond. As used herein, the term substituted means that at least one hydrogen atom on a particular atom or group is replaced by another group, provided that the normal valence of that particular atom is not exceeded. The term substituted with a group means substitution with one or more groups.

As used herein, oxyalkylene includes groups of the formula HO-R ¹¹ where R ¹¹ is a C ₂ -C ₁₀ alkylene group (including oxirane and methyl oxirane), in particular ethylene, propylene, isopropylene or butylene.

As used herein, the polyoxyalkylene group has the formula H-[OR ¹⁰ -]z, where in each occurrence R ¹⁰ is independently C1-10 alkylene, in particular ethylene, propylene, isopropylene, butylene, and oxirane and methyloxirane, or a combination thereof, az is an integer greater than 1, such as 2 to 30, 4 to 25, or 8 to 25. Additionally, the polyoxyalkylene group may be a homopolymer or copolymer having the formula H(OR ⁿ )x-[OR ⁿ -]y, where x and y are independently selected from the range of 1 to 1500, and each R ¹¹ is independently as defined above. For example, a polyoxyalkylene group may have the formula H(OCH2CH2) _x (CH2CHCH ₃ O) _y .

The alkylene-polyoxyalkylene group has the formula -R ¹² -[OR ¹³ -]y, where R ¹² is C 1-30 alkylene (including oxirane and methyl oxirane), in each case R ¹³ is independently C _1-10 alkylene or C ₂ _ ₆ alkylene (including oxirane and methyloxirane), in particular ethylene, propylene, isopropylene or butylene, and y is an integer from 1 to 500, for example from 2 to 30, from 4 to 25 or from 8 to 25.

The alkylene-oxyalkylene group has the formula -R ¹⁴ -OR ¹⁵ -, wherein R ¹⁴ and R ¹⁵ are each independently C _1-20 or C _1-10 or C _1-5 branched or straight chain alkylene (including oxirane and methyloxirane). In a particular embodiment, R ¹⁴ and R ¹⁵ are ethylene.

In one embodiment, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is -H or C _1-20 alkyl. In one embodiment, at least one of the R groups is C _6-20 alkyl, and in another embodiment, at least one of the R groups is C _6-12 alkyl. In another embodiment, each of the at least two R groups is independently C _2-20 alkyl. In another embodiment, each of the at least two R groups is independently C _6-20 alkyl. In yet another embodiment, at least one R group is C _6-20 alkyl and at least one of the remaining R groups is C _1-6 alkyl or C _1-3 alkyl. In yet another embodiment, each of the at least two R groups is independently C _6-20 alkyl and at least one of the remaining R groups is C _1-6 alkyl or C _1-3 alkyl. In a further embodiment, each of the at least two R groups is independently C _6-20 alkyl and at least two remaining R groups are C _1-6 alkyl or C _1-3 alkyl.

Preferably, the ionic liquids are basic ionic liquids. Used in this document, ionic liquids, as a rule, are salts with a melting point below 100°C. They have a low vapor pressure and are less harmful to the environment than other organic solvents such as volatile aromatic hydrocarbons and alkanes. The properties of ionic liquids can be adapted by selecting the appropriate

- 6 041390 combinations of anion and cation for specific applications. Specific examples of basic ionic liquids include, without limitation, dicocodimethylammonium hydroxide, ditallow dimethylammonium hydroxide, tributylmethylammonium methyl carbonate, tetraethylammonium bicarbonate, tetrabutylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, hydrogenated tallow trimethylammonium hydroxide, dihydrogenated tallow dimethylammonium bismethylammonium hydroxide, cooxydiethylammonium or a combination of them. As a rule, dicocodimethylammonium hydroxide, ditallow dimethylammonium hydroxide are indicated. As used herein, oxydiethylene bis(cocodimethylammonium hydroxide) refers to an ionic liquid having the structure represented by the formula: koko(CH3) ₂ N ⁺ (CH2)2O(CH2)2N ⁺ (CH3) ₂ koko(OH') ₂ .

In one embodiment, ionic liquids having the dicocodimethylammonium and ditallow dimethylammonium cation are preferred.

The ionic liquid may be combined with a treatment agent capable of inhibiting, reducing or preventing the formation or agglomeration of asphaltene deposits. The treatment agent may further be characterized by the ability to inhibit, reduce or prevent the precipitation of asphaltenes in the petroleum hydrocarbon fluid. In one embodiment, the treatment may be capable of inhibiting, reducing, or preventing precipitation from the petroleum hydrocarbon fluid.

The treatment agent may be an asphaltene stabilizer and/or an asphaltene inhibitor known in the art to reduce deposition and address asphaltene-related fluid handling problems. As noted above, the ionic liquids described herein, when used in conjunction with an asphaltene treatment agent, improve the stabilization and inhibition of asphaltenes.

Suitable asphaltene inhibitors include, without limitation, phenolic resins, homopolymers and copolymers of fatty acid esters (such as esters of polymers and copolymers of acrylic and methacrylic acids), and sorbitan monooleate, alkoxylated fatty amines and fatty amine derivatives, optionally in combination with organic metal salt.

Phenol-aldehyde resins include polymers or oligomers derived from substituted monophenols or unsubstituted monophenols and an aldehyde. Monophenol substituents may be attached to the para, ortho, or both positions of the monophenol. Preferably the substituents are attached to the para position of the monophenol. The substituted monophenol may be an alkyl-substituted monophenol. The alkyl may be branched (an alkyl group with an alkyl substituent). Alkyl substituents include C _1-20 , C _4-18 or C _4-12 branched or straight alkyl groups.

Phenolic aldehyde resins can be prepared from a monophenol, or from combinations of two or more different substituted monophenols, or an unsubstituted monophenol and an aldehyde. The molar ratio of two or more different substituted monophenols or unsubstituted monophenol is not particularly limited.

A branched alkyl phenol may refer to any of its branched isomers or combinations thereof. For example, branched alkylphenol may refer to any of its branched substituent isomers or any combination of such isomers.

Examples of phenols with branched alkyl groups include branched dodecylphenol, branched nonylphenol, t-butylphenol, t-amylphenol, and branched hexylphenols such as 4-(1-methylpentyl)phenol, 4-(1,2-dimethylbutyl)phenol, 4-(1 -ethyl, 2-methylpropyl)phenol, 4-(1,3dimethylbutyl)phenol and 4-(1-ethylbutyl)phenol and phenol.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, glutaraldehyde, 1,9-nonandial, or a combination thereof. As a rule, formaldehyde is indicated.

In one embodiment, phenolic resins are made from formaldehyde and a monophenol, and have the following formula:

R ^J n where R is C _1-20 , C _4-18 or C _4-12 branched or linear alkyl groups and n is an integer greater than 1, typically greater than 2. In a preferred embodiment, R is C _{6 -20} alkyl.

If phenolic resins are derived from two or more phenols that are either unsubstituted or substituted with specific alkyl branches, the phenolics derived from them (mixed phenolics) can provide higher levels of effectiveness as asphaltene stabilizers (and when inhibiting the adverse effects of asphaltenes) compared to a phenolic resin made from phenol alone.

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Examples of mixed phenolic aldehydes include polymers derived from an aldehyde and two or more of a substituted monophenol or an unsubstituted monophenol, containing a first phenol that is a C1-20 linear or branched alkyl monophenol; and a second phenol which is an unsubstituted or _{C1_20} linear or branched alkyl monophenol other than the first phenol.

In one embodiment, the mixed phenolic aldehydes are derived from _{C7_20} linear or branched alkyl monophenol and C _1-6 linear or branched alkyl monophenol. In another embodiment, the mixed phenolic aldehydes are derived from C ₉ _ ₁₂ linear or branched alkyl monophenol and C _1-6 linear or branched alkyl monophenol.

In specific embodiments, mixed phenolic aldehydes are derived from the following combinations of phenols: branched 4-dodecylphenol and p-tert-butylphenol; branched 4-nonylphenol and p-tert-butylphenol; branched 4-dodecylphenol and branched 4-hexylphenol; or branched 4-nonylphenol and branched 4-hexylphenol.

In one embodiment, the mixed phenol formaldehydes have the following formula:

where R ⁵ is C1.20 (preferably C7-20) linear or branched alkyl, R ⁶ is different from R ⁵ and is H or C1_20 (preferably C _1-6 ) linear or branched alkyl, n and m are integers numbers greater than 1. In one embodiment, R ⁵ is C9_12 straight or branched alkyl, and R ⁶ is C1-6 straight or branched alkyl. In a specific embodiment, R ⁵ is dodecyl and R ⁶ is t-butyl; or R ⁵ is straight or branched dodecyl and R ⁶ is branched hexyl; or R ⁵ is nonyl and R ⁶ is t-butyl; or R ⁵ is dodecyl and R ⁶ is methyl. The n:m value can vary widely, such as from about 99:1 to about 1:99, from about 1:20 to about 20:1, or from about 1:10 to about 10:1. In one embodiment, the value of n:m is from about 1:5 to about 5:1. In one embodiment, the value of n:m is from about 4:1 to about 1:4. Optionally, in some embodiments, the n:m value can be from about 3:1 to about 1:3, from about 2.8:1 to about 1:2.8, from about 2.5:1 to about 1:2, 5, from about 2.3:1 to about 1:2.3, or from about 2:1 to about 1:2.

When the molar ratio of two or more alkyl-substituted monophenols is from about 4:1 to about 1:4 (in some embodiments, optionally from about 2:1 to about 1:2), the mixed phenolic aldehydes may further exhibit superior efficacy in inhibiting unwanted effects of asphaltenes. For example, a mixed phenol aldehyde made from a first phenol and a second phenol having a molar ratio of about 4:1 to about 1:4 (in some embodiments, optionally about 2:1 to about 1:2) may provide better stabilization. asphaltenes and prevent the undesirable effects of asphaltenes when compared to a control phenolic aldehyde derived from the first phenol only, derived from the second phenol only, or derived from both the first and second phenols but having a molar ratio outside the range of about 4: 1 to about 1:4 (in some embodiments, optionally from about 2:1 to about 1:2).

When two or more phenols are used, mixed phenolic aldehydes derived from them can achieve greater chain length and higher weight average molecular weight than phenolic aldehydes prepared in similar ways using a monosubstituted alkyl monophenol. The weight average molecular weight of the mixed phenolic aldehydes can be from about 5,000 to about 20,000 daltons, or from about 6,000 to about 10,000 daltons, each measured by gel permeation chromatography (GPC) using a column packed with a cross-linked styrene-divinylbenzene copolymer .

Methods for preparing mixed phenolic aldehydes include reacting an aldehyde with two or more monophenols as described herein in the presence of an acid catalyst such as a sulfonic acid (eg, dodecylbenzenesulfonic acid), oxalic acid, or hydrochloric acid. If desired, an antifoam agent may be added. The molar ratio of aldehyde to the sum of moles of two or more monophenols is from about 0.4:1 to about 1.2:1. The reaction temperature may be from about 90°C to about 140°C. The reaction of the aldehyde with the mixed phenols is generally carried out in about 30 minutes to about 4 hours, in particular less than about 3 hours.

Known additives can be added to increase the effectiveness of the asphaltene inhibitor, for example to reduce the deposition and accumulation of asphaltenes. In one embodiment, more

- 8 041390 High stabilization of asphaltenes can be achieved by mixing phenolic resin or mixed phenolic resins with a synergist such as amines and polyamines. In one embodiment, blended phenolics when used together with synergists exhibit superior asphaltene stabilization compared to compounds of the same synergistic additive with phenolics derived from phenol alone.

Examples of synergistic additives include imidazoline, which is a fatty acid derivative, diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine, or a combination thereof. In one embodiment, the synergistic(e) additive(s) are used in doses of from about 1 to about 25% of the amount of phenolic aldehydes, based on weight. In another embodiment, the weight ratio of mixed phenol-aldehyde to synergistic additive is from about 99:1 to about 4:1.

The amounts of ionic liquids and asphaltene inhibitor may be determined depending on the particular phenolic resin used, the particular chemistry of petroleum hydrocarbon fluids, and the conditions such as pressure and temperature to which petroleum hydrocarbon fluids are exposed during production, processing and storage.

In one embodiment, the amount of ionic liquid added to the petroleum hydrocarbon fluid is from about 1 ppm to about 2000 ppm, or from about 1 ppm to about 500 ppm, or from about 5 hours/million to about 150 hours/million based on the total volume of petroleum hydrocarbon fluid. The amount of asphaltene inhibitor added to the petroleum hydrocarbon fluid is from about 5 ppm to about 5000 ppm, or from about 10 ppm to about 1000 ppm, or from about 25 ppm up to about 500 ppm, based on the total volume of petroleum hydrocarbon fluid. In the asphaltene inhibitor composition, the amount of asphaltene inhibitor relative to the ionic liquid on a weight basis is about 99:1, or about 9:1, or about 3:1. In one embodiment, the asphaltene inhibitor compositions contain from about 5 to about 65 wt.% or from about 10 to about 50 wt.% asphaltene inhibitor and from about 1 to about 15 wt.% or from about 1 wt.% to about 7, 5 wt.% ionic liquid, each based on the total weight of the asphaltene inhibitor compositions.

It should be understood that both the ionic liquids and the asphaltene inhibitor can be added to petroleum hydrocarbon fluids in the form of solutions or dispersions. The amounts stated herein are based on the volume of the ionic liquids themselves and the asphaltene inhibitor, and not on the volume of the ionic liquid/asphaltene inhibitor solutions or dispersions that contain the solvent for the asphaltene inhibitor and/or ionic liquids.

The ionic liquids and the asphaltene inhibitor may be added to petroleum hydrocarbon fluids separately. In an alternative embodiment, the ionic liquids and phenolic resins can first be combined to form an asphaltene inhibitor composition and then contact the asphaltene inhibitor composition with petroleum hydrocarbon fluids.

In addition to ionic liquids and phenolic resins, asphaltene inhibitor compositions may additionally contain other components in their formulations. These components can be included to provide formulations having the desired physical or stability characteristics for injection or storage process conditions. Examples of formulation components include solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones, and aldehydes. The asphaltene inhibitor compositions can be prepared in various forms, including, without limitation, solutions, dispersions, emulsions, and the like. Depending on the form of the asphaltene inhibitor compositions, additives such as water, surfactants, dispersants, emulsifiers, or combinations thereof may be present.

Other examples of additives to provide additional benefits include dispersants, corrosion inhibitors, scale inhibitors, wax inhibitors, hydrate inhibitors, demulsifiers, sulfur scavengers, or a combination thereof. Any known dispersants, corrosion inhibitors, scale inhibitors, paraffin inhibitors, hydrate inhibitors, demulsifiers, and sulfur scavengers may be used, provided that these additives do not adversely affect the effectiveness of inhibition of asphaltenes by the ionic liquid and phenolic resin compounds.

The amount of asphaltene inhibitor compositions used to treat petroleum hydrocarbon fluids in an asphaltene inhibitor composition may vary depending on the concentrations of the ionic liquid and the asphaltene inhibitor, the particular chemistry of the petroleum hydrocarbon fluids, and the conditions such as pressure and temperature to which the petroleum products are exposed. hydrocarbon fluids during production, processing, processing and storage. In one embodiment, from about 10 ppm to about 10,000 ppm, or from about 50 ppm to about 5,000 ppm, or from about 100 ppm to about 1000 ppm asphaltene inhibitor compositions.

Examples

The following examples illustrate some of the embodiments of the present invention. Other embodiments within the scope of the claims will be apparent.

- 9 041390 to a person skilled in the art based on the description provided in this document. It is intended that the description, together with the examples, be taken as exemplary only, and that the scope and spirit of the invention are set forth in the claims below.

One way to evaluate asphaltene inhibitors is to measure asphaltene stability using the technique described in US Pat. No. 9,360,425, also referred to as Analytical Centrifuge Stability Analysis for Asphaltenes (ACSAA). The ACSAA method combines the use of an analytical centrifuge with the process of adding a destabilizing solvent to a petroleum hydrocarbon fluid to quantify the relative instability of asphaltenes in a particular hydrocarbon fluid. Thus, the effect of asphaltene inhibitors on reducing the relative instability of asphaltenes in a hydrocarbon fluid can be measured by the ACSAA method and then used to compare the relative performance of asphaltene inhibitors with each other.

The measured instability index determined by the ACSAA method is called the instability index. This is the normalized value of sample instability, ranging from 0 to 1. A value of zero indicates no instability (no change or complete stability during the test), while a value of 1 indicates maximum change or instability.

Asphaltene inhibitors that provide the greatest reduction in instability index compared to untreated or control samples are rated as more effective inhibitory chemicals or products. In the examples below, the percentage increase (or percentage decrease) in the instability index is presented in tables and graphs for various samples of crude oils treated with the ionic liquid/phenol-aldehyde compounds of the present invention, and, for comparison purposes in control examples, for various samples of crude oils. treated with pure phenolic aldehydes and phenolic compounds with currently used amines and polyamines in the industry.

The ACSAA test can be carried out at various temperatures. When testing at higher temperatures, the petroleum hydrocarbon fluid, destabilizing solvent, and centrifuge tubes are preheated prior to mixing the hydrocarbon fluid and destabilizing solvent. After that, they are mixed, and then immediately placed in an analytical centrifuge maintained at the test temperature, and analysis is carried out. The analytical centrifuge used in this work has a maximum operating temperature of 60°C. However, the effect of slightly higher temperatures can be obtained by heating the samples (hydrocarbon fluid, destabilizing solvent, centrifuge tubes, etc.) to a higher temperature, mixing the hydrocarbon fluid and solvent, and then centrifuging them at 60°C. For example, for some of the data below, the temperature is pseudo 80°C. In these experiments, the samples were heated to 90°C in an oven, immediately mixed after removal from the oven, and then analyzed in an analytical centrifuge at 60°C.

Examples 1-6. Examples 1-6 demonstrate the effect of various ionic liquids as synergists in improving the effectiveness of the asphaltene inhibitor based on phenolic resin No. 1, prepared from a monophenol monophenol, as described herein, in increasing the instability index compared to the test (control) of untreated crude oil by the ACSAA method at 25°C for sample No. 1 of crude oil. Also shown is the result obtained using an industrial polyamine additive. Compositions and results are summarized in table. 1. The results are also graphically presented in FIG. 1.

Table 1

Component Unit. Wed pr. 1 Wed n.p. 2 Etc. 3 Etc. 4 Etc. 5 Etc. 6 Phenol-aldehyde resin No. 1 PPm too too 100 100 100 100 Polyamine PPm 200 Dicocodimethylammonium hydroxide PPm 200 Ditallium dimethylammonium hydroxide PPm 200 Tributylmethylammonium methyl carbonate PPm 200 Tetraethylammonium bicarbonate PPm 200 Efficiency Improvement over control % 58.5 65.1 69.4 62.7 79.2 76.0

'Added phenolic resin No. 1 was a 40 wt% solution 2' Added ionic liquids and polyamine were 5 wt% solutions

As shown in Table. 1 and in FIG. 1, each of the ionic liquids tested (Example 3-Example 6) when used with Phenolic Resin #1 provides some improvement over the performance of Phenolic Resin #1 without the synergist (Comparative Example 1). In addition, dicocodimethylammonium hydroxide (Example 3), tributylmethylammonium methyl carbonate (Example 5) and tetraethylammonium bicarbonate (Example 6) are more effective than the polyamine additive (Comparative Example 2).

- 10 041390

Examples 7-11. Examples 7-11 demonstrate the effect of two different ionic liquids (dicocodimethylammonium hydroxide and ditallow dimethylammonium hydroxide) as synergists in increasing the effectiveness of a phenolic resin asphaltene inhibitor No. 2 prepared from two alkyl-substituted monophenols as described herein to increase the index instability compared to the test (control) crude oil ACSAA at 25°C for sample No. 1 crude oil. Results are also shown using industrially used polyamine and amine additives. Compositions and results are summarized in table. 2. The results are also graphically presented in FIG. 2.

table 2

Component Unit. Wed pr. 7 Wed etc. 8 Wed etc. 9 Etc. 10 Etc. eleven Phenol-aldehyde resin No. 2 ppt 100 100 100 100 100 Amine PPm 200 Polyamine PPm 200 Dicocodimethylammonium hydroxide PPm 200 Ditallic hydroxide dimethylammonium PPm 200 Efficiency Improvement over control 0/ /0 48.4 34.6 49.0 66.8 71.9

1‘Added phenolic resin No. 2 was a 40 wt.% solution ^Added ionic liquids, amine and polyamine were 5 wt.% solutions

The results show that the amine has an adverse effect on the performance of phenolic resin No. 2 on this crude oil. Phenolic resin No. 2 without any additive showed an improvement over crude oil by about 48.4% (Comparative Example 7). However, when using phenolic resin No. 2 together with an amine, the improvement over crude oil is reduced to 34.6% (Comparative Example 8). Polyamine does not significantly affect the performance of Phenolic Resin No. 2, as the improvement over crude oil with polyamine is 49% (comparative example 9), while the improvement over crude oil in the absence of synergist is 48% (comparative example 7). In contrast, when using the ionic liquid described herein, the efficiency of phenolic resin No. 2 increased significantly from 48.4% (Comparative Example 7) to 66.8% (Example 10) and 71.9% (Example 11). Both tested ionic liquids (example 10 and example 11) are also much more effective than amine and polyamine additives (comparative example 8 and comparative example 9).

Examples 12-19. Examples 12-19 demonstrate the effect of various ionic liquids as synergists to increase the effectiveness of an asphaltene inhibitor based on phenolic resin No. 3, obtained from a monophenol other than the monophenol used to produce phenolic resin No. 1, to increase the instability index by compared to the ACSAA 25° C. crude oil test for crude oil No. 2. The results obtained using an industrial amine additive are also shown. Compositions and results are summarized in table. 3. The results are also graphically presented in FIG. 3.

Table 3

Component Unit. cp. n.p. 12 cp. n.p. 13 Etc. 14 Etc. 15 Etc. 16 Etc. 17 Etc. 18 Etc. 19 Phenol-aldehyde resin No. 3 PPm 100 100 100 100 100 100 100 100 Amine PPm 150 Tributylmethylammonium methyl carbonate PPm 150 Tetrabutylammonium hydroxide PPm 150 Tetraethylammonium bicarbonate PPm 150 Hydroxide dicodimethylammonium PPm 150 Ditallic hydroxide dimethylammonium PPm 150 Oxydiethylene bis(cocodimethylammonium hydroxide) PPm 150 Efficiency Improvement over control % 23.6 36.4 27.7 24.4 25.6 48.5 49.3 26.5

1'Added phenolic resin No. 3 was a 40 wt.% solution ^Added ionic liquids and amine were 5 wt.% solutions

As shown in Table. 3 and in FIG. 3, each of the tested ionic liquids (example 14 - example

- 11 041390

19) when used together with Phenolic Resin #3 provides some improvement over the performance of Phenolic Resin #3 without the synergist (comparative example

12). In addition, dicocodimethylammonium hydroxide (Example 17) and ditallow dimethylammonium hydroxide (Example 18) are more effective than the amine additive (Comparative Example 13).

Examples 20-26. Examples 20-26 demonstrate the effect of various ionic liquids as synergists in improving the effectiveness of the asphaltene inhibitor based on phenolic resin No. 3 in increasing the instability index compared to the test of untreated crude oil by the ACSAA method at 25 ° C for crude oil No. 3. Compositions and the results are summarized in table. 4. The results are also graphically presented in FIG. 4.

Table 4

Component Unit. Wed n.p. 20 Etc. 21 Etc. 22 Etc. 23 Etc. 24 Etc. 25 Etc. 26 Phenol-aldehyde resin No. 3 ppm 400 400 400 400 400 400 400 Tributylmethylammonium methyl carbonate ppm 400 Tetrabutylammonium hydroxide ppm 400 Tetraethylammonium bicarbonate ppm 400 Dicocodimethylammonium hydroxide ppm 400 Ditallic hydroxide dimethylammonium ppm 400 Oxydiethylene bis(cocodimethylammonium hydroxide) ppm 400 Efficiency Improvement over control O/ /O 18.7 63.7 56.0 50.0 65.1 72.0 41.2

1‘Added phenolic resin No. 3 was a 40 wt.% solution ^Added ionic liquids were 5 wt.% solutions

As shown in Table. 4 and in FIG. 4, each of the ionic liquids tested (Example 21-Example 26) when used together with Phenolic Resin No. 3 provides a significant improvement in performance over Phenolic Resin No. 3 without the synergist (Comparative Example 20).

Examples 27-30. Examples 27-30 demonstrate the effect of an ionic liquid, namely, ditallium dimethylammonium hydroxide as a synergist, and an industrial amine additive to increase the effectiveness of a phenol resin asphaltene inhibitor No. 2 and a phenolic resin asphaltene inhibitor No. 4, which derived from the same two alkyl substituted monophenols used to make Phenolic Resin #2, but with a different ratio of monophenols, to increase the instability index compared to the ACSAA test of crude oil at 25, 60 and pseudo 80°C for crude oil # 4. Compositions and results are summarized in table. 5A and 5B. The results are also graphically presented in FIG. 5.

Table 5A

Component Unit. Wed project 27 Etc. 28 Phenol-aldehyde resin No. 2 ppt 1000 1000 Amine PPm 750 Ditallium dimethylammonium hydroxide PPm 750 Efficiency Improvement compared to control (25°C) % 42.6 48.2 Improvement compared to control (60°C) O/ /O 34.0 38.8 Improvement compared to control (80°C) O/ /O 24.4 51.3

1' Phenol Resin No. 2 used was a 40 wt% solution ² Ionic liquids and amine were 10 wt% solutions

Table 5B

Component Unit. Wed project 29 Etc. thirty Phenol-aldehyde resin No. 4 PPm 1000 1000 Amine PPm 750 Ditallium dimethylammonium hydroxide PPm 750 Efficiency Improvement compared to control (25°C) % 30.0 41.8 Improvement compared to control (60°C) O/ /O 28.2 43.6 Improvement compared to control (80°C) O/ /O 31.1 52.3

1' Phenol Resin No. 4 used was a 40 wt% solution ² Ionic liquids and amine were 10 wt% solutions

The results show that ditallow dimethylammonium hydroxide (Example 28 and Example 30) provides better performance than the amine additive for both Phenolic Resin No. 2 and Phenolic Resin No. 4 (Comparative Example 27 and Comparative Example 29) at all

- 12 041390 test temperatures of 25, 60 and pseudo 80°C. This improvement is more noticeable at elevated temperatures. When using the amine additive, the improvement from the No. 2 phenolic resin compared to the crude oil tested at 80° C. is 24.4% (Comparative Example 27). Conversely, when ditallow dimethylammonium hydroxide was used at the same loading level, the improvement from phenolic resin No. 2 compared to crude oil tested at 80°C is 51.3% (Example 28), i.e. more than double the improvement provided by the amine additive. Similarly, a comparison of Comparative Example 29 and Example 30 showed that when using an amine additive, the improvement from phenolic resin No. 4 compared to crude oil tested at 80°C was 31.1%, and when using ditallic hydroxide dimethylammonium at the same loading level, the improvement from phenolic resin No. 4 compared to crude oil tested at 80°C was 52.3%.

Examples 31-33. Examples 31-33 demonstrate the effect of ionic liquids, namely dicocodimethylammonium hydroxide and ditallow dimethylammonium hydroxide, as synergists in improving the effectiveness of the asphaltene inhibitor based on phenolic resin No. 2 in increasing the instability index compared to testing untreated crude oil by the ACSAA method at 25, 60 and pseudo 80°C for crude oil No. 4. Compositions and results are summarized in table. 6. The results are also graphically presented in FIG. 6.

Table 6

Component Unit. Wed project 31 Etc. 32 Etc. 33 Phenol-aldehyde resin No. 2 ppm 1000 1000 1000 Dicocodimethylammonium hydroxide PPm 1000 Ditallium dimethylammonium hydroxide 1000 Efficiency Improvement compared to control (25°C) o/ /o 0.7 38.3 37.3 Improvement compared to control (60°C) o/ /o 10.6 33.5 34.0 Improvement compared to control (80°C) o/ /o 10.9 35.8 36.3

¹ Phenol Resin #2 used was 40 wt% solution ² Ionic liquids were 10 wt% solutions

As shown in Table. 6 and in FIG. 6, each of the tested ionic liquids (Example 32 and Example 33) when used together with Phenolic Resin #2 improves the performance of Phenolic Resin #2 without the synergist (Comparative Example 31) at all test temperatures of 25, 60 and pseudo 80°C.

Examples 34-37. Examples 34-37 demonstrate the effect of ionic liquids, namely dicocodimethylammonium hydroxide and ditallow dimethylammonium hydroxide, as synergists to increase the effectiveness of asphaltene inhibitors based on phenolic resin No. 2 in increasing the instability index compared to testing untreated crude oil by ACSAA at 25, 60 and pseudo 80°C for crude oil No. 4. Also shown are the results obtained using an industrial amine additive.

Table 7

Component Unit. Wed project 34 Wed project 35 Etc. 36 Etc. 37 Phenol-aldehyde resin No. 2 PPm 1000 1000 1000 1000 Amine PPm 1000 Dicocodimethylammonium hydroxide PPm 1000 Ditallium dimethylammonium hydroxide PPm 1000 Efficiency Improvement compared to control (25°C) % 0.7 62.4 38.3 37.5 Improvement compared to control (60°C) o/ /o 10.6 27.1 33.5 34.0 Improvement compared to control (80°C) o/ /o 10.9 14.5 35.8 36.3

¹ Phenol Resin No. 2 used was a 40 wt% solution ² Ionic liquids and amine were 10 wt% solutions

As shown in Table. 7 and in FIG. 7, each of the tested ionic liquids (Example 36 to Example 37) when used together with Phenolic Resin No. 2 improves the performance of Phenolic Resin No. 2 without a synergist (Comparative Example 34). At 25°C, ionic liquids, namely dicocodimethylammonium hydroxide and ditallow dimethylammonium hydroxide (example 36 - example 37) show no better performance than the amine synergist (comparative example 35). However, at higher temperatures, each of these compounds demonstrates significantly higher efficiency than the amine additive.

The methods that may be described above or claimed in the claims herein, and any other methods that may be within the scope of the following claims, may be performed in any suitable order desired and are not necessarily limited in any way.

- 13 041390 sequence described in this document, or a possible list in the following claims. In addition, the methods of the present description do not necessarily require the application of specific embodiments presented and described herein, and are equally applicable to any other suitable structure, shape and configuration of the components.

Although examples of implementation are presented and described in this specification, many variations, modifications and/or changes to the system, apparatus and methods of the present disclosure are possible, for example, in components, details of construction and operation, location of parts and/or methods of application, which are envisaged by the applicant (s). ) of the patent are within the scope of the following claims and can be made and used by a person skilled in the art without departing from the spirit or ideas of the present description and the scope of the following claims. Thus, all features set forth herein or shown in the accompanying drawings should be interpreted as illustrative, and the scope of the present description and the following claims should not be limited to the embodiments described and shown herein.

Embodiment 1. A method for improving the effectiveness of an asphaltene inhibitor in the production, storage, transportation, or processing of a petroleum hydrocarbon fluid, comprising contacting the asphaltene inhibitor with an ionic liquid during a production or processing operation, or before or during storage or transportation of the petroleum hydrocarbon fluid, wherein the ionic the liquid has a cation R ¹ R ² R ³ R ⁴ N ⁺ or R ¹ R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen, straight or branched C1.30αalkyl group, benzyl, C7.3oalkylbenzyl group, C7.30arylalkyl group, straight or branched C3.3oalkenyl group, C1.30hydroxyalkyl group, C7.30hydroxyalkylbenzyl group, oxyalkylene or a polyoxyalkylene group or a zwitterion; R ⁸ is straight or branched C1. ₃₀ αkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

Embodiment 2. The method of Embodiment 1 wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is -H or C ₁ . ₂₀ alkyl.

Embodiment 3. The method of Embodiment 2 wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is C ₆ . ₂₀ alkyl.

Embodiment 4. The method of Embodiment 3 wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is C ₆ . ₁₂ alkyl.

Embodiment 5. The method of any one of Embodiments 2-4, wherein at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are C ₂ . ₂₀ alkyl.

Embodiment 6. The method of Embodiment 5 wherein at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently C ₆ . ₂₀ alkyl.

Embodiment 7. The method of any one of Embodiments 1-6, wherein the polyoxyalkylene group has the formula H-[OR ¹⁰ -]z, where R ¹⁰ is independently a C1-10 alkylene at each occurrence, az is an integer greater than 1 .

Embodiment 8. The method of Embodiment 7 wherein C ₁ . ₁₀ alkylene is ethylene, propylene, butylene, or a combination thereof.

Embodiment 9. The method of Embodiment 7 or 8 wherein z is between 2 and 30.

Embodiment 10. The method of any one of Embodiments 1-6, wherein the alkylene polyoxyalkylene group has the formula -R ¹² -[OR ¹³ -]y, wherein R ¹² is C1-30 alkylene, R ¹³ is independently alkylene at each occurrence. C _1-10 and y is an integer from 1 to 500.

Embodiment 11. The method of Embodiment 10 wherein the C _1-10 alkylene is ethylene, propylene, butylene, or a combination thereof.

Embodiment 12. The method of any one of Embodiments 1-6, wherein the alkyleneoxyalkylene group has the formula -R ¹⁴ -OR ¹⁵ -, wherein R ¹⁴ and R ¹⁵ are each independently C _1-20 branched or straight chain alkylene.

Embodiment 13. The method of any one of Embodiments 1-12 wherein the anion is a hydroxide.

Embodiment 14. The method of any one of Embodiments 1-12 wherein the anion is a carbonate or a bicarbonate.

Embodiment 15. The method of Embodiment 14 wherein the anion is an alkyl carbonate of the formula ROCO2 ^- where R is a halogenated or non-halogenated straight or branched alkyl or hydroxyalkyl group.

Embodiment 16. The method of Embodiment 15 wherein the anion is an alkyl carbonate selected from the group consisting of methyl, ethyl, propyl, butyl, 2-ethylhexyl, octyl, ethylene, and propylene carbonate.

- 14 041390

Embodiment 17. The method of any one of Embodiments 1-12 wherein the anion is a carboxylate, hydroxycarboxylate, or C ₁₈ fatty acid, or a combination thereof.

Embodiment 18. The method of Embodiment 17 wherein the anion is selected from the group consisting of formate, acetate, propionate, benzoate, n-butyrate, isobutyrate, pivalate, octanoate, laurate, glycolate, lactate, citrate, glucarate, gluconate, oleate , linoleate and stearate, or combinations thereof.

Embodiment 19. The method of any one of Embodiments 1-12 wherein the anion is an alkoxide.

Embodiment 20. The method of Embodiment 19 wherein the alkoxide has the formula RO- where R is C ₁ . ₃₀ alkyl or cycloalkyl group.

Embodiment 21. The method of Embodiment 20 wherein R is C ₁ . ₁₈ αkyl, C6. ₁₂ aryl or C ₅ . ₁₂ cycloalkyl.

Embodiment 22. The method of Embodiment 21 wherein the anion is an alkoxide selected from the group consisting of t-butoxide, n-butoxide, isopropoxide, npropoxide, isobutoxide, ethoxide, methoxide, n-pentoxide, isopentoxide, 2-ethylhexoxide , 2 propyl heptoxide, nonoxide, octoxide, decoxide, and their isomers, or combinations thereof.

Embodiment 23. The method of Embodiment 19 wherein the alkoxide is an ethylene or propylene oxide homopolymer, copolymer or terpolymer that is optionally cross-linked.

Embodiment 24. The method of Embodiment 1 wherein the ionic liquid comprises dicocodimethylammonium hydroxide, ditallow dimethylammonium hydroxide, tributylmethylammonium methyl carbonate, tetraethylammonium bicarbonate, tetrabutylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, hydrogenated tallow trimethylammonium hydroxide, dihydrogenated tallow trimethylammonium hydroxide, cocodimethylammonium hydroxide) or a combination thereof.

Embodiment 25. The method of any one of Embodiments 1-24 wherein the weight ratio of asphaltene inhibitor to ionic liquid is from about 99:1 to about 3:1.

Embodiment 26. The method of any one of Embodiments 1-25, wherein the asphaltene inhibitor is selected from the group consisting of fatty acid ester homopolymers, fatty acid ester copolymers, sorbitan monooleate, phenolic resins, alkoxylated fatty amines, fatty amine derivatives, or their combinations.

Embodiment 27 The method of Embodiment 25 or 26 wherein the asphaltene inhibitor is combined with an organic metal salt.

Embodiment 28 The method of Embodiment 26 wherein the asphaltene inhibitor is a phenolic resin.

Embodiment 29. The method of Embodiment 28 wherein the asphaltene inhibitor further comprises an amine or polyamine additive.

Embodiment 30. The method of Embodiment 29 wherein the amine or polyamine additive is selected from the group consisting of imidazolines which are fatty acid derivatives, diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine, or a combination thereof.

Embodiment 31. The method of any one of Embodiments 28-30, wherein the phenol-aldehyde resin is derived from an alkyl-substituted monophenol or an unsubstituted monophenol, or a combination thereof, and an aldehyde.

Embodiment 32. The method of Embodiment 31 wherein the alkyl substituted monophenol has a branched or linear C ₁ . _{The 20} alkyl substituent, or a combination thereof, and the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, glutaraldehyde, 1,9-nonandial, or a combination thereof.

Embodiment 33. The method of any one of Embodiments 28-30, wherein the phenolic resin has the structure:

He

where R represents -H or linear or branched C ₁ . ₂₀ alkyl and n is greater than 2.

Embodiment 34. The method of Embodiment 33 wherein at least one R is C ₆ . ₂₀ αkil.

- 15 041390

Embodiment 35. The method of any one of Embodiments 28-30, wherein the phenolic resin has a structure represented by the formula:

G ON Ί G ON Ί

where R ⁵ is linear or branched C1.20 alkyl, R ⁶ is different from R ⁵ and is H or linear or branched C1. ₂₀ alkyl, and n and m are greater than 1.

Embodiment 36. The method of Embodiment 35 wherein R ⁵ is straight or branched C7.16 alkyl and R ⁶ is straight or branched C1. ₆ alkyl.

Embodiment 37. The method of any one of Embodiments 1-36 wherein the ionic liquid and the asphaltene inhibitor form a complex.

Embodiment 38. The method of any one of Embodiments 1-36 wherein the ionic liquid and the asphaltene inhibitor form a synergistic mixture.

Embodiment 39. The method of Embodiment 37 or 38 wherein the weight ratio of asphaltene inhibitor to ionic liquid in the complex or synergistic mixture is from about 5:95 to about 3:1.

Embodiment 40. The method of any one of Embodiments 1-36 wherein the ionic liquid and the asphaltene inhibitor form a reaction product.

Embodiment 41. The method of Embodiment 40 wherein the reaction product is formed from the reaction of an asphaltene inhibitor and an ionic liquid in a weight ratio of from about 5:95 to about 3:1.

Embodiment 42 An asphaltene inhibitor composition comprising an asphaltene inhibitor and an ionic liquid containing a cation R1R ² R ³ R ⁴ N ⁺ or R1R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen, straight or branched C1.30 alkyl group, benzyl, C7.30 alkylbenzyl group, C7.30 arylalkyl group, straight or branched C3.30 alkenyl group, C1 .30 hydroxyalkyl group, C7.30 hydroxyalkylbenzyl group, oxyalkylene or polyoxyalkylene group or zwitterion; R ⁸ is straight or branched C1. ₃₀ alkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

Embodiment 43 The asphaltene inhibitor composition of Embodiment 42 wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ is -H or C ₁ . ₂₀ alkyl.

Embodiment 44 The asphaltene inhibitor composition of Embodiment 43 wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ is C ₆ . ₂₀ alkyl.

Embodiment 45 The asphaltene inhibitor composition of Embodiment 44, wherein at least one of R1, ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , and ^R7 is _C6 . ₁₂ alkyl.

Embodiment 46 The asphaltene inhibitor composition of any one of Embodiments 43-45, wherein at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are C ₂ . ₂₀ alkyl.

Embodiment 47 The asphaltene inhibitor composition of Embodiment 46, wherein at least two of R1, ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , and ^R7 are independently _C6 . ₂₀ alkyl.

Embodiment 48 The asphaltene inhibitor composition of any one of Embodiments 42-47, wherein the polyoxyalkylene group has the formula H-[OR ¹⁰ -]z, where R ¹⁰ is independently C1 at each occurrence. ₁₀ alkylene, az is an integer greater than 1.

Embodiment 49. The asphaltene inhibitor composition of Embodiment 48 wherein C ₁ . ₁₀ alkylene is ethylene, propylene, butylene, or a combination thereof.

Embodiment 50 The asphaltene inhibitor composition of Embodiment 48 or 49 wherein z is between 2 and 30.

Embodiment 51 The asphaltene inhibitor composition of Embodiment 42-47, wherein the alkylene-polyoxyalkylene group has the formula -R ¹² -[OR ¹³ -]y, where R ¹² is C1. ₃₀ alkylene, R ¹³ is independently C ₁ at each occurrence. ₁₀ is alkylene and y is an integer from 1 to 500.

Embodiment 52. The asphaltene inhibitor composition of Embodiment 51 wherein C ₁ . ₁₀ alkylene is ethylene, propylene, butylene, or a combination thereof.

Embodiment 53 The asphaltene inhibitor composition of any one of Embodiments 42-47, wherein the alkylene-oxyalkylene group has the formula -R ¹⁴ -OR ¹⁵ -, where R ¹⁴ and R ¹⁵ are each independently C ₁ . ₂₀ branched or straight chain alkylene.

- 16 041390

Embodiment 54. The asphaltene inhibitor composition of any one of Embodiments 42-53, wherein the anion is a hydroxide.

Embodiment 55 The asphaltene inhibitor composition of any one of Embodiments 42-53, wherein the anion is a carbonate or a bicarbonate.

Embodiment 56 The asphaltene inhibitor composition of Embodiment 55 wherein the anion is an alkyl carbonate of the formula ROCO2 ^- where R is a halogenated or non-halogenated linear or branched alkyl or hydroxyl alkyl group.

Embodiment 57 The asphaltene inhibitor composition of Embodiment 56 wherein the anion is an alkyl carbonate selected from the group consisting of methyl, ethyl, propyl, butyl, 2-ethylhexyl, octyl, ethylene, and propylene carbonate.

Embodiment 58. The asphaltene inhibitor composition of any one of Embodiments 42-53, wherein the anion is a carboxylate, hydroxycarboxylate, or C ₁₈ fatty acid, or a combination thereof.

Embodiment 59. The asphaltene inhibitor composition of Embodiment 58 wherein the anion is selected from the group consisting of formate, acetate, propionate, benzoate, n-butyrate, isobutyrate, pivalate, octanoate, laurate, glycolate, lactate, citrate, glucarate, gluconate , oleate, linoleate and stearate, or combinations thereof.

Embodiment 60. The asphaltene inhibitor composition of any one of Embodiments 42-53, wherein the anion is an alkoxide.

Embodiment 61 The asphaltene inhibitor composition of Embodiment 60, wherein the alkoxide has the formula RO-, where R is C ₁ . ₃₀ alkyl or cycloalkyl group.

Embodiment 62 The asphaltene inhibitor composition of Embodiment 61 wherein R is C ₁ . ₁₈ alkyl, C ₆ . ₁₂ aryl or C5. ₁₂ cycloalkyl.

Embodiment 63. The asphaltene inhibitor composition of Embodiment 62 wherein the anion is an alkoxide selected from the group consisting of t-butoxide, n-butoxide, isopropoxide, n-propoxide, isobutoxide, ethoxide, methoxide, n-pentoxide, isopentoxide, 2 -ethylhexoxide, 2-propylheptoxide, nonoxide, octoxide, decoxide and their isomers or combinations thereof.

Embodiment 64. The asphaltene inhibitor composition of Embodiment 60, wherein the alkoxide is an ethylene oxide or propylene oxide homopolymer, copolymer, or terpolymer, which is optionally cross-linked.

Embodiment 65. The asphaltene inhibitor composition of Embodiment 42, wherein the ionic liquid comprises dicocodimethylammonium hydroxide, ditallow dimethylammonium hydroxide, tributylmethylammonium methyl carbonate, tetraethylammonium bicarbonate, tetrabutylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, hydrogenated tallow trimethylammonium hydroxide, dimethylhydrogenated dimethylammonium hydroxide oxydiethylene bis(cocodimethylammonium hydroxide) or a combination thereof.

Embodiment 66. The asphaltene inhibitor composition of any one of embodiments 42-65, wherein the asphaltene inhibitor to ionic liquid weight ratio is from about 99:1 to about 3:1.

Embodiment 67. The asphaltene inhibitor composition of any one of Embodiments 42-66, wherein the asphaltene inhibitor is selected from the group consisting of fatty acid ester homopolymers, fatty acid ester copolymers, sorbitan monooleate, phenolic resin, alkoxylated fatty amine, fatty acid derivative, amine.

Embodiment 68 The asphaltene inhibitor composition of Embodiment 67 wherein the asphaltene inhibitor is optionally combined with an organic metal salt.

Embodiment 69 The asphaltene inhibitor composition of Embodiment 67, wherein the asphaltene inhibitor is a phenolic resin.

Embodiment 70. The asphaltene inhibitor composition of Embodiment 69, wherein the asphaltene inhibitor further comprises an amine or polyamine additive.

Embodiment 71. The method of Embodiment 70 wherein the amine or polyamine additive is selected from the group consisting of imidazolines which are fatty acid derivatives, diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine, or a combination thereof.

Embodiment 72 The asphaltene inhibitor composition of any one of Embodiments 69-71, wherein the phenolic resin is derived from an alkyl-substituted monophenol or an unsubstituted monophenol, or a combination thereof, and an aldehyde.

Embodiment 73 The asphaltene inhibitor composition of Embodiment 72 wherein the alkyl substituted monophenol has a branched or linear C ₁ . ₂₀ alkyl substituent or a combination thereof, and aldehyde includes formaldehyde, paraformaldehyde, acetaldehyde, propional dehyde, butyraldehyde, glyoxal, glutaraldehyde, 1,9-nonandial, or a combination thereof.

Embodiment 74 The asphaltene inhibitor composition of any one of Embodiments 69-71, wherein the phenolic resin has the structure:

where R is -H or linear or branched C ₁ _ ₂₀ alkyl and n is greater than 2.

Embodiment 75. The asphaltene inhibitor composition of Embodiment 74 wherein at least one R is C _{6 -20} alkyl.

Embodiment 76 The asphaltene inhibitor composition of any one of Embodiments 69-71, wherein the phenolic resin has a structure represented by the formula:

where R ⁵ is straight or branched Cl_20 alkyl, R ⁶ is different from R ⁵ and is H or straight or branched Cl_20 alkyl, and n and m are greater than 1.

Embodiment 77 The asphaltene inhibitor composition of Embodiment 76 wherein R ⁵ is straight or branched C7_l6 alkyl and R ⁶ is straight or branched Cl_6 alkyl.

Embodiment 78 The asphaltene inhibitor composition of any one of Embodiments 42-77 wherein the ionic liquid and the asphaltene inhibitor form a complex.

Embodiment 79 The asphaltene inhibitor composition of any one of Embodiments 42-77 wherein the ionic liquid and the asphaltene inhibitor form a synergistic mixture.

Embodiment 80. The asphaltene inhibitor composition of embodiment 78 or 79 wherein the weight ratio of asphaltene inhibitor to ionic liquid in the complex or synergistic mixture is from about 5:95 to about 3:1.

Embodiment 81 The asphaltene inhibitor composition of any one of Embodiments 42-77, wherein the ionic liquid and the asphaltene inhibitor form a reaction product.

Embodiment 82 The asphaltene inhibitor composition of Embodiment 81, wherein the reaction product is formed from the reaction of the asphaltene inhibitor and the ionic liquid in a weight ratio of about 5:95 to about 3:1.

Embodiment 83. Petroleum hydrocarbon fluid containing the asphaltene inhibitor composition of any one of Embodiments 42-82.

Embodiment 84. The petroleum hydrocarbon fluid of Embodiment 83, which is crude oil, bitumen, diesel fuel, coking distillate, alkylate, reformate, cycle oil, hydrotreated hydrocarbon, fuel oil, biofuel, residual oil, fuel gas, flare gas, propane, butane, liquefied petroleum gas (LPG), natural gas liquid (NGL), or refinery component.

Embodiment 85. The petroleum hydrocarbon fluid of embodiment 83 or 84 wherein the amount of ionic liquid is from about 5 ppm to about 150 ppm based on the total volume of petroleum hydrocarbon fluid.

Embodiment 86. The petroleum hydrocarbon fluid of embodiment 83 or 84 wherein the amount of the asphaltene inhibitor composition is from about 25 ppm to about 500 ppm based on the total volume of the petroleum hydrocarbon fluid.

Embodiment 87. A method of increasing the production of petroleum hydrocarbon fluid from a subterranean formation in which a well is drilled, the method includes injecting into the well an asphaltene inhibitor composition according to any one of embodiments 42-82.

Embodiment 88. A method of inhibiting, reducing or preventing the formation, agglomeration and/or accumulation of asphaltene deposits, or inhibiting, preventing or reducing the precipitation of asphaltenes from a petroleum hydrocarbon fluid (a) in a subterranean reservoir; (b) in a pipeline or column, or (iii) in a refinery by contacting the fluid with the asphaltene inhibitor composition of any one of embodiments 42-82.

Embodiment 89. A method of improving the stability of a petroleum hydrocarbon fluid, comprising contacting the petroleum hydrocarbon fluid with an as-falten inhibitor composition according to any one of embodiments 42-82.

Embodiment 90. The method of any one of embodiments 87-89, wherein the ionic liquid and the asphaltene inhibitor are complexed prior to contacting the ionic liquid and the asphaltene inhibitor with a petroleum hydrocarbon fluid.

Embodiment 91. The method of any one of embodiments 87-89, wherein the ionic liquid and the asphaltene inhibitor form a complex after contacting the ionic liquid and the asphaltene inhibitor with a petroleum hydrocarbon fluid.

Embodiment 92. The method of any one of Embodiments 42-82 wherein the ionic liquid and the asphaltene inhibitor form a synergistic mixture.

Embodiment 93. The method of any one of Embodiments 90-92, wherein the weight ratio of asphaltene inhibitor to ionic liquid in the complex or synergistic mixture is from about 5:95 to about 3:1.

Embodiment 94. The method of any one of Embodiments 42-82 wherein the ionic liquid and the asphaltene inhibitor form a reaction product.

Embodiment 95. The method of Embodiment 94 wherein the reaction product is formed from the reaction of an asphaltene inhibitor and an ionic reactant in a weight ratio of from 5:95 to about 3:1.

Embodiment 96. The method of embodiment 88 or 89 wherein the petroleum hydrocarbon fluid is contacted with the asphaltene inhibitor composition prior to loading the petroleum hydrocarbon fluid onto the vehicle.

Embodiment 97. The method of any one of embodiments 88 or 89, wherein the petroleum hydrocarbon fluid is contacted with the asphaltene inhibitor composition during transportation of the petroleum hydrocarbon fluid in a vehicle.

Embodiment 98. The method of any one of embodiments 87-97 wherein the petroleum hydrocarbon fluid is crude oil, bitumen, diesel fuel, coker distillate, alkylate, reformate, cycle oil, hydrotreated hydrocarbon, light oil fuel, biofuel, residual oil, fuel gas, flare gas, propane, butane, liquefied petroleum gas (LPG), natural gas liquid (NGL), or refinery component.

Embodiment 99. The method of Embodiment 98 wherein the petroleum hydrocarbon fluid is crude oil or bitumen.

Embodiment 100. A method for treating a petroleum hydrocarbon fluid, comprising: contacting the petroleum hydrocarbon fluid with a phenolic resin and an ionic liquid containing the cation R1R ² R ³ R ⁴ N ⁺ or R1R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen, straight or branched C1.30 alkyl group, benzyl, C7.30 alkylbenzyl group, C7. a 30 arylalkyl group, a straight or branched C3.30 alkenyl group, a C1.30 hydroxyalkyl group, a C7.30 hydroxyalkylbenzyl group, an oxyalkylene or polyoxyalkylene group, or a zwitterion; R ⁸ is straight or branched C1. ₃₀ alkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

Embodiment 101. The method of Embodiment 100 wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ is C ₁ . ₂₀ alkyl.

Embodiment 102. The method of Embodiment 101 wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ is C ₆ . ₂₀ alkyl.

Embodiment 103. The method of Embodiment 101 or 102 wherein at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are C ₆ . ₂₀ alkyl.

Embodiment 104. The method of any one of Embodiments 100-103 wherein the basic anion is a hydroxide.

Embodiment 105. The method of Embodiment 100 wherein the ionic liquid comprises dicocodimethylammonium hydroxide, ditallow dimethylammonium hydroxide, tributylmethylammonium methyl carbonate, tetraethylammonium bicarbonate, tetrabutylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, hydrogenated tallow trimethylammonium hydroxide, ethylenebimethylimmonium dihydrogenated cocodimethylammonium hydroxide) or a combination thereof.

Embodiment 106. The method of any one of embodiments 100-105 wherein the amount of ionic liquid is from about 5 ppm to about 150 ppm based on the total volume of petroleum hydrocarbon fluid.

Embodiment 107. The method of any one of Embodiments 100-106, wherein the phenolic resin is derived from an alkyl-substituted monophenol or an unsubstituted monophenol and an aldehyde.

Embodiment 108. The method of Embodiment 107 wherein the alkyl substituted monophenol has a branched or linear C ₁ . _{The 20} alkyl substituent, or a combination thereof, and the al dehyde include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, glutaraldehyde, 1,9-nonandial, or a combination thereof.

Embodiment 109. The method of Embodiment 107 or 108, wherein the phenolic resin has the structure represented by the formula

where R ⁵ is linear or branched C1.20 alkyl, R ⁶ is different from R ⁵ and is H or linear or branched C1. ₂₀ alkyl, and n and m are greater than 1.

Embodiment 110. The method of Embodiment 109 wherein R ⁵ is straight or branched C7.16 alkyl and R ⁶ is straight or branched C1. ₆ alkyl.

Embodiment 111. The method of any one of embodiments 100-110, wherein the amount of phenolic resin is from about 25 ppm to about 500 ppm based on the total volume of petroleum hydrocarbon fluid.

Embodiment 112. The method of any of embodiments 100-111 wherein the petroleum hydrocarbon fluid further comprises water, brine, gas, or a combination thereof.

Embodiment 113. The method of any one of embodiments 100-112, wherein the contacting occurs during production, storage, transportation, or processing of petroleum hydrocarbon fluid.

Embodiment 114. The method of any one of embodiments 100-113, wherein the contacting is carried out at a temperature of from about -50° C. to about 250° C. and at a pressure of about 14.7 psig abs. up to about 40,000 psi abs.

Embodiment 115. The method of any one of Embodiments 100-114, wherein the phenolic aldehyde and the ionic liquid are separately added to the petroleum hydrocarbon fluid.

Embodiment 116. The method of any one of embodiments 100-115, further comprising combining a phenolic aldehyde with an ionic liquid to form an asphaltene inhibitor composition and adding the asphaltene inhibitor composition to the petroleum hydrocarbon fluid.

Embodiment 117 An asphaltene inhibitor composition comprising a phenolic resin and an ionic liquid having a cation R1R ² R ³ R ⁴ N ⁺ or R1R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from hydrogen, straight or branched C1.30 alkyl group, benzyl, C7.30 alkyl benzyl group, C7.30 arylalkyl group, straight or branched C3.30 alkenyl group, C1 .30 hydroxyalkyl group, C7.30 hydroxyalkylbenzyl group, oxyalkylene or polyoxyalkylene group or zwitterion; R ⁸ is straight or branched C1. ₃₀ αkylene, alkyleneoxyalkylene or alkylenepolyoxyalkylene; and the anion includes halides, hydroxyl, bicarbonate, carbonate, alkyl carbonates, alkoxides, carboxylates, hydroxycarboxylates, or combinations thereof.

Embodiment 118. The asphaltene inhibitor composition of Embodiment 117, wherein the weight ratio of phenolic resin to ionic liquid is from about 99:1 to about 3:1.

Embodiment 119. The asphaltene inhibitor composition of Embodiment 117 or 118, wherein at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , or R ⁷ is C ₆ . ₂₀ alkyl.

Embodiment 120. The asphaltene inhibitor composition of Embodiment 119, wherein at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , or R ⁷ are C ₆ . ₂₀ αkil.

Embodiment 121. The asphaltene inhibitor composition of Embodiment 117 or 118, wherein the ionic liquid comprises dicocodimethylammonium hydroxide, ditallium dimethylammonium hydroxide, tributylmethylammonium methyl carbonate, tetraethylammonium bicarbonate, tetrabutylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, hydrogenated tallium dimethylammonium hydroxide, hydroxide hydrogenated thallium dimethylammonium hydroxide dimethylammonium, oxydiethylene bis(cocodimethylammonium hydroxide), or a combination thereof.

Embodiment 122 The asphaltene inhibitor composition of any one of Embodiments 100-121, wherein the phenolic resin is derived from an alkyl-substituted monophenol or an unsubstituted monophenol, or a combination thereof, and an aldehyde.

Claims (18)

CLAIM 1. A method for improving the effectiveness of an asphaltene inhibitor in the production, storage, transportation or processing of a petroleum hydrocarbon fluid, comprising bringing the asphaltene inhibitor into contact with an ionic liquid during a production or processing operation or before or during storage or transportation of a petroleum hydrocarbon fluid, where the ionic liquid has cation R1R ² R ³ R ⁴ N ⁺ or R1R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion, where R ⁸ is a straight or branched C1-30 alkylene or polyoxyalkylene group of the formula -R ¹⁴ -OR ¹⁵ - where each of R ¹⁴ and R ¹⁵ is independently a branched or straight chain C1-20 alkylene, a polyoxyalkylene group of the formula -R ¹² -[ OR ¹³ -]y, where R ¹² is C1-30 alkylene, R ¹³ is independently C1-10 alkylene at each occurrence, and y is an integer from 2 to 30; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from (a) hydrogen, straight or branched C _1-30 alkyl group, benzyl, C _7-30 alkylbenzyl group, C _{7- 30} arylαalkyl group, straight or branched C _3-30 alkenyl group, C _1-30 hydroxyαalkyl group, C _7-30 hydroxyalkylbenzyl group; and (b) a polyoxyalkylene of the formula H-[OR ¹⁰ -]z, where R ¹⁰ is at each occurrence independently C _2-10 alkylene and z is an integer greater than 2; and the anion includes (i) a halide; hydroxyl; bicarbonate or carbonate; (ii) an alkyl carbonate of the formula R1OCO2 ^- where R1 is a halogenated or non-halogenated linear or branched C1- _C8 alkyl or hydroxyalkyl group; (iii) an alkoxide of the formula RO-, where R is a C _1-30 alkyl or cycloalkyl group, or a homopolymer, copolymer or terpolymer of ethylene oxide or propylene oxide, which is optionally cross-linked; (iv) a carboxylate selected from the group consisting of formates, acetate, propionates, octanoates, laurates, benzoates, n-butyrates, isobutyrates and pivalates; and a C ₁₈ fatty acid carboxylate; (v) a hydroxycarboxylate selected from the group consisting of glycolate, lactate, citrate, glucarate and gluconate, or combinations thereof; or the ionic liquid is a compound selected from dicocodimethylammonium hydroxide, ditallow dimethylammonium hydroxide, tributylmethylammonium methyl carbonate, tetraethylammonium bicarbonate, tetrabutylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, hydrogenated tallow trimethylammonium hydroxide, dihydrogenated tallow trimethylammonium hydroxide, or a combination of them; and wherein the weight ratio of asphaltene inhibitor to ionic liquid is from 99:1 to 3:1. 2. The method according to claim 1, in which R ¹⁰ is ethylene, propylene, butylene, or a combination thereof, and z is an integer from 2 to 30, or polyoxyalkylene (b) is a homopolymer or copolymer of the formula ^OR^-EO-R ¹¹ -]^ where x and y independently selected from the range of 1 to 1500 and each R ¹¹ is a C ₂ -C ₁₀ alkylene group, preferably R ¹¹ is ethylene, propylene, isopropylene or butylene, and R ¹³ is ethylene, propylene, butylene, or a combination thereof. 3. The method of claim 1 wherein the asphaltene inhibitor is selected from the group consisting of fatty acid ester homopolymers, fatty acid ester copolymers, sorbitan monooleate, phenolic resins, alkoxylated fatty amines, fatty amine derivatives, or combinations thereof. 4. The method of claim 3, wherein the asphaltene inhibitor is a phenolic resin, preferably either: ^(A) where R is -H or linear or branched C _1-20 alkyl, preferably wherein at least one R is C _6-20 alkyl and n is greater than 2; or - 21 041390 (b) where R ⁵ represents a linear or branched C 1-2 o alkyl, preferably a linear or branched N ^ alkyl, and R ⁶ is different from R ⁵ and represents H or a linear or branched C _1-20 alkyl, preferably a linear or branched C _1-6 alkyl , and n and m are greater than 1. 5. The method of claim 1 wherein the asphaltene inhibitor is a phenolic resin and further comprises an amine or polyamine additive which is preferably selected from the group consisting of fatty acid imidazolines, diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine, or combinations thereof. 6. A process according to any one of claims 1 to 5, wherein the ionic liquid and the asphaltene inhibitor form a synergistic mixture. 7. An asphaltene inhibitor composition containing an asphaltene inhibitor and an ionic liquid having a cation R1R ² R ³ R ⁴ N ⁺ or R1R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and an anion, where R ⁸ is a straight or branched C1.30α alkylene or polyoxyalkylene group of the formula —R ¹⁴ —OR ¹⁵ — wherein R ¹⁴ and R ¹⁵ are each independently branched or straight chain C1-20 alkylene; a polyoxyalkylene group of the formula -R ¹² -[OR ¹³ -]y, where R ¹² is _{C1_30} αkylene, R ¹³ is independently C _{1_10} alkylene at _each occurrence, and y is an integer from 2 to 30; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from: (a) hydrogen, straight or branched C ₁ _ ₃₀ alkyl group, benzyl, C ₇ . ₃₀ αalkylbenzyl group, C ₇ _ ₃₀ arylalkyl group, straight or branched C ₃ . ₃₀ alkenyl group, C ₁ . ₃₀ hydroxyalkyl group, C ₇ . ₃₀ hydroxyalkylbenzyl group; and (b) a polyoxyalkylene of the formula H-[OR ¹⁰ -]z, where R ¹⁰ is independently C2 at each occurrence. ₁₀ αkylene, and z is an integer greater than 2; and the anion includes (i) a halide; hydroxyl; bicarbonate or carbonate; (ii) an alkyl carbonate of the formula R1OCO2 ^- where R1 is a halogenated or non-halogenated linear or branched C1- _C8 alkyl or hydroxyalkyl group; (iii) an alkoxide of the formula RO-, where R is a C ₁ _ ₃₀ alkyl or cycloalkyl group, or a homopolymer, copolymer or terpolymer of ethylene oxide or propylene oxide, which is optionally cross-linked; (iv) a carboxylate selected from the group consisting of formates, acetate, propionates, octanoates, laurates, benzoates, n-butyrates, isobutyrates and pivalates; and C ₁₈ fatty acid carboxylate; (v) a hydroxycarboxylate selected from the group consisting of glycolate, lactate, citrate, glucarate and gluconate, or combinations thereof; or the ionic liquid is a compound selected from dicocodimethylammonium hydroxide, ditallow dimethylammonium hydroxide, tributylmethylammonium methyl carbonate, tetraethylammonium bicarbonate, tetrabutylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, hydrogenated tallow trimethylammonium hydroxide, dihydrogenated tallow trimethylammonium hydroxide, or a combination of them. 8. The asphaltene inhibitor composition of claim 7, wherein R ¹⁰ is ethylene, propylene, butylene, or a combination thereof, and z is an integer from 2 to 30, or polyoxyalkylene (b) is a homopolymer or copolymer of the formula H(OR ¹¹ )x-[OR ¹¹ -]y, where x and y are independently selected from the range of 1 to 1500 and each R ¹¹ is a C ₂ -C ₁₀ alkylene group, preferably R ¹¹ is ethylene, propylene, isopropylene or butylene and R ¹³ is ethylene, propylene, butylene or their combination. 9. The asphaltene inhibitor composition of claim 7 wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is hydrogen or C 1 -C ₂₀ alkyl. 10. The asphaltene inhibitor composition of claim 7, wherein the asphaltene inhibitor is a phenolic resin, preferably either - 22 041390 (a) where R is -H or linear or branched C ₁ _ ₂₀ alkyl, preferably wherein at least one R is C ₆ _ ₂₀ alkyl and n is greater than 2; either (b) where R ⁵ is linear or branched C1-20 alkyl, preferably linear or branched C 7-16 alkyl, and R ⁶ is different from R ⁵ and is H or linear or branched C 1-20 alkyl, preferably linear or branched C _1-6 alkyl, and n and m are greater than 1. 11. The asphaltene inhibitor composition of claim 7, wherein the asphaltene inhibitor is a phenolic resin and further comprises an amine or polyamine additive which is preferably selected from the group consisting of fatty acid imidazolines, diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine, or a combination thereof. . 12. An asphaltene inhibitor composition according to any one of claims 7 to 11, wherein the ionic liquid and the asphaltene inhibitor form a synergistic mixture. 13. A petroleum hydrocarbon fluid containing an asphaltene inhibitor composition according to any one of claims 7 to 12, wherein at least one of the following conditions is met: (a) petroleum hydrocarbon fluid is crude oil, bitumen, diesel fuel, coker distillate, alkylate, reformate, cycle oil, hydrotreated hydrocarbon, light fuel oil, biofuel, residual oil, fuel gas, flare gas, propane, butane, liquefied petroleum gas (LPG), natural gas liquid (NGL) or refinery component; (b) the amount of ionic liquid is from 5 to 150 ppm based on the total volume of petroleum hydrocarbon fluid; or (c) the amount of the asphaltene inhibitor composition is from 25 to 500 ppm based on the total volume of petroleum hydrocarbon fluid. 14. The use of an asphaltene inhibitor composition according to any one of claims 7 to 12 for inhibiting, reducing or preventing the formation, agglomeration and/or accumulation of asphaltene deposits or inhibiting, preventing or reducing the precipitation of asphaltenes from petroleum hydrocarbon fluid (i) in a subterranean reservoir; (ii) in a pipeline or column, or (iii) in a refinery by contacting the fluid with the asphaltene inhibitor composition. 15. The use of claim 14, wherein the ionic liquid and the asphaltene inhibitor are synergistically blended such that the mixture is formed prior to contacting the ionic liquid and the asphaltene inhibitor with the petroleum hydrocarbon fluid. 16. The use of claim 14 wherein the petroleum hydrocarbon fluid is crude oil, bitumen, diesel fuel, coking distillate, alkylate, reformate, cycle oil, hydrotreated hydrocarbon, light oil fuel, biofuel, residual oil, fuel gas, flare gas, propane, butane, liquefied petroleum gas (LPG), natural gas liquid (NGL), or a refinery component. 17. A method for treating a petroleum hydrocarbon fluid, comprising bringing the petroleum hydrocarbon fluid into contact with a phenol-aldehyde resin and an ionic liquid having a cation R^R^N or R ¹ R ² R ³ N ⁺ R ⁸ N ⁺ R ⁵ R ⁶ R ⁷ and anion, where R ⁸ is a straight or branched C1_30 alkylene or polyoxyalkylene group of formula -R14-OR ¹⁵ - where R ¹⁴ and R ¹⁵ are each independently _{C1_20} branched or straight chain alkylene; a polyoxyalkylene group of the formula -R ¹² -[OR ¹³ -]y, where R ¹² is _{C1_30} alkylene, R ¹³ is independently C _{1_10} alkylene at _each occurrence, and y is an integer from 2 to 30; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently selected from (a) hydrogen, straight or branched C ₁ _ ₃₀ alkyl group, benzyl, - 23 041390 C _7-30 alkylbenzyl group, C _7-30 arylalkyl group, straight or branched C _3-30 alkenyl group, C _1-30 hydroxyalkyl group, C _7-30 hydroxyalkylbenzyl group, (b) a polyoxyalkylene of the formula H-[OR ¹⁰ -]z, where R ¹⁰ in each occurrence independently represents C _2-10 alkylene, and z is an integer greater than 2; and the anion includes (i) a halide; hydroxyl; bicarbonate or carbonate; (ii) an alkyl carbonate of the formula R ₁ OCO ₂ ^- where R ₁ is a halogenated or non-halogenated linear or branched C1-C ₈ alkyl or hydroxyalkyl group; (iii) an alkoxide of the formula RO-, where R is a C _1-30 alkyl or cycloalkyl group, or a homopolymer, copolymer or terpolymer of ethylene oxide or propylene oxide, which is optionally cross-linked; (iv) a carboxylate selected from the group consisting of formates, acetate, propionates, octanoates, laurates, benzoates, n-butyrates, isobutyrates and pivalates; and a C ₁₈ fatty acid carboxylate; (v) a hydroxycarboxylate selected from the group consisting of glycolate, lactate, citrate, glucarate and gluconate, or combinations thereof. 18. The method according to claim 17, in which R ¹⁰ is ethylene, propylene, butylene, or a combination thereof, and z is an integer from 2 to 30, or polyoxyalkylene (b) is a homopolymer or copolymer of the formula H(OR ¹¹ )x-[OR ¹¹ -]y, where x and y are independently selected from 1 to 1500 and each R ¹¹ is a C2-C ₁₀ alkylene group, preferably R ¹¹ is ethylene, propylene, isopropylene or butylene and R ¹³ is ethylene, propylene, butylene or their combination. ACSAA Test Results - No. 1 Phenolic Resin with Synergist Crude Oil No. 1 15 vol% in heptane/cyclohexane, 100/200 ppm dosage z 80.0% o About 70.0% about S 60.0% £50.0% m 2. 40.0% o o 30.0% 2 $20.0-.