Polyetheramine salts and their use as corrosion inhibitors and friction reducers

Abstract

The present invention relates generally to a fuel additive composition for reducing corrosion and wear of internal combustion engines or fuel constituent parts thereof. The fuel additive composition comprises a polyetheramine salt obtained by (a) mixing a polyalkylene oxide monoamine with at least one of a dicarboxylic acid or a tricarboxylic acid, or (b) mixing a polyalkylene oxide polyamine with at least one of a monocarboxylic acid, a dicarboxylic acid or a tricarboxylic acid.

Description

[0001] This application is a divisional application. The parent application was filed on August 27, 2021, with application number 202180063113.4 and invention title "Polyetheramine Salt and its Use as Corrosion Inhibitor and Friction Reducer".

[0002] Cross-references to related applications

[0003] This application claims priority to U.S. Provisional Application 63 / 079,155, filed September 16, 2020, which is incorporated herein by reference.

[0004] Statement regarding federally funded research or development

[0005] not applicable. Technical Field

[0006] This invention generally relates to fuel additive compositions comprising a polyetheramine salt obtained by: (a) mixing a polyoxyethylene monoamine with at least one of a dicarboxylic acid or a tricarboxylic acid; or (b) mixing a polyoxyethylene polyamine with at least one of a monocarboxylic acid, a dicarboxylic acid, or a tricarboxylic acid. This fuel additive composition can be used as a corrosion inhibitor and friction modifier in fuel compositions containing hydrocarbon-containing compositions. Background Technology

[0007] Regulatory agencies in many countries have been pushing hard to reduce vehicle emissions by lowering the sulfur content in fuels. This reduction process also removes many aromatic and polar molecules that are added to fuel to increase its lubricity and thus reduce wear on fuel pumps and injectors. Correspondingly, the absence of these molecules significantly reduces the durability of fuel pumps and injectors. Furthermore, gasoline direct injection (GDI) engines have recently replaced port fuel injection (PFI) engines, where the higher pressures and temperatures encountered in this fuel delivery system further exacerbate engine wear problems.

[0008] In addition, corrosion inhibitors are often added to fuel to prevent corrosion of tanks, pipelines, and engines. Corrosion in tank and pipeline systems often stems from water contamination in the fuel. In the case of gasoline-oxide blends, corrosion problems can also arise from acidic impurities present in oxygenated fuels. While effective in reducing corrosion, these inhibitors typically exhibit little friction-reducing property to counteract the aforementioned problems.

[0009] While existing corrosion inhibitors and friction reducers may be suitable for specific applications, there is still a need to develop alternative compounds that can provide corrosion inhibition and friction reduction without introducing undesirable side effects to fuel systems and engines using these compounds when added to fuel at low concentrations. Summary of the Invention

[0010] The present invention generally provides a fuel additive composition for reducing corrosion and increasing lubricity of hydrocarbon-containing compositions in contact with fuel system components or internal combustion engines, the fuel additive composition comprising a polyetheramine salt obtained by: (a) mixing a polyoxyethylene monoamine with at least one of dicarboxylic acid or tricarboxylic acid; or (b) mixing a polyoxyethylene polyamine with at least one of monocarboxylic acid, dicarboxylic acid or tricarboxylic acid.

[0011] In another embodiment, a corrosion and friction-inhibiting fuel composition comprising the fuel additive composition of the present invention and a hydrocarbon-containing composition is provided.

[0012] In another embodiment, a method is provided for preventing corrosion and reducing wear on metal, plastic, or synthetic parts or surfaces of fuel system components or internal combustion engines, the method comprising combining an effective amount of a fuel additive composition with a hydrocarbon-containing composition to form a fuel composition, and bringing the metal, plastic, or synthetic part or surface into contact with the fuel composition during engine operation. Detailed Implementation

[0013] This invention generally relates to fuel additive compositions comprising a polyetheramine salt obtained by: (a) mixing a polyoxyethylene monoamine with at least one of a dicarboxylic acid or a tricarboxylic acid; or (b) mixing a polyoxyethylene polyamine with at least one of a monocarboxylic acid, a dicarboxylic acid, or a tricarboxylic acid. Surprisingly, it has been found that when the fuel additive compositions of this invention are added to hydrocarbon-containing compositions, the amount of corrosion forming on surfaces in contact with the hydrocarbon-containing composition can be prevented or significantly reduced. Furthermore, it has been surprisingly found that when the fuel additive compositions are added to hydrocarbon-containing compositions, the lubricity of the hydrocarbon-containing composition is increased, and thus wear on internal combustion engine surfaces or fuel system components in contact with or having been in contact with the hydrocarbon-containing composition can be greatly reduced. In some embodiments, the versatile nature of the fuel additive compositions according to the invention allows them to be used substantially without any additional prior art corrosion inhibitors or friction modifiers.

[0014] Therefore, using this fuel additive composition in a hydrocarbon-containing composition during internal combustion engine operation can significantly reduce corrosion and wear around fuel system components and engine piston walls. This reduction in friction should further result in improved fuel economy. Wear and corrosion of fuel system components and internal combustion engines limit their service life and can lead to significant losses given their high production costs. Furthermore, this corrosion and wear can cause downtime, reduced safety, and decreased reliability, while using the fuel additive composition can reduce this corrosion and wear, thereby increasing the service life of these components and the engine.

[0015] The following terms should have the following meanings:

[0016] The term “comprising / including” and its derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are disclosed herein. For the avoidance of any ambiguity, unless stated to the contrary, all compositions claimed herein may contain any additional additives, auxiliaries, or compounds when using the term “comprising / including.” Conversely, if it appears herein, the term “consistently comprising” excludes any other components, steps, or procedures from the scope of any subsequent description except those not essential to operability, and if used, the term “consisting of” excludes any components, steps, or procedures not specifically described or listed. Unless otherwise stated, the term “or” refers to the individually listed members and any combination thereof.

[0017] The articles “a” and “an” are used herein to refer to one or more (i.e., at least one) grammatical object of the article. For example, “a polyetheramine” refers to one or more polyetheramines. Expressions such as “in one embodiment” or “according to one embodiment” generally indicate that the specific feature, structure, or characteristic following the expression is included in at least one embodiment of the invention and may be included in more than one embodiment of the invention. Importantly, these expressions do not necessarily refer to the same aspect. If the specification states that a component or feature “may,” “can,” “can,” or “may” be included or have a certain characteristic, it is not required that the specific component or feature be included or have that characteristic.

[0018] As used herein, the term “about” allows for a certain degree of variation in a value or range, for example, it may be within 10%, 5%, or 1% of the limits of the value or range.

[0019] Numerical values ​​expressed as ranges should be interpreted flexibly, including not only the values ​​explicitly described as range boundaries, but also all individual values ​​or subranges encompassed within that range, as if each value and subrange were explicitly described. For example, a range (such as 1-6) should be considered to include specifically disclosed subranges such as 1-3, 2-4, 3-6, etc., as well as individual values ​​within that range, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the extent of the range.

[0020] The terms "preferred" and "preferred" refer to embodiments that provide certain benefits under certain conditions. However, other embodiments may also be preferred under the same or other conditions. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are useless, nor is it intended to exclude other embodiments from the scope of the invention.

[0021] The term "hydrocarbon composition" refers to petroleum (crude oil) or liquid fuels such as gasoline, diesel, biodiesel, kerosene, naphtha, water-fuel emulsions, ethanol-based fuels, and ether-based fuels.

[0022] As used in this article, the term "fuel system components" refers to all accessories that intervene in and connect to the fuel system of an internal combustion engine (engine), including, for example, fuel tanks, fuel filters, fuel pumps, etc.

[0023] The term “corrosion” refers to any degradation, rusting, weakening, deterioration, or softening of any surface, including tanks, pipes, engine surfaces, or fuel system components, resulting from exposure to or combustion of a hydrocarbon-containing composition.

[0024] The term “corrosion inhibition” or “corrosion reduction” refers to any improvement in minimizing, reducing, eliminating or preventing corrosion.

[0025] The term “friction reduction” or “friction reduction” refers to the reduction of frictional losses caused by friction between a hydrocarbon composition and a storage tank, pipeline, engine surface, or fuel system component due to exposure to or combustion of a hydrocarbon composition.

[0026] The term "alkyl" includes straight-chain or branched saturated aliphatic hydrocarbons having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl (1-methylethyl), butyl, tert-butyl (1,1-dimethylethyl), etc.

[0027] The term "alkenyl" includes unsaturated aliphatic hydrocarbon chains having 2 to 24 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, etc.

[0028] The aforementioned alkyl or alkenyl groups can be terminally substituted with heteroatoms (such as nitrogen, sulfur, or oxygen atoms) to form aminoalkyl, oxyalkyl, or thioalkyl groups (e.g., aminomethyl, thioethyl, propoxy, etc.). Similarly, the aforementioned alkyl or alkenyl groups can be broken in the chain by heteroatoms to form alkylaminoalkyl, alkylthioalkyl, or alkoxyalkyl groups (e.g., methylaminoethyl, ethylthiopropyl, methoxymethyl, etc.).

[0029] The term "alicyclic" includes any cyclic hydrocarbon group containing 3 to 8 carbon atoms. Examples of suitable alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, etc.

[0030] The term "heterocyclic" includes any cyclic hydrocarbon group containing 3 to 8 carbon atoms that is broken by a heteroatom (such as a nitrogen atom, sulfur atom, or oxygen atom). Examples of heterocyclic groups include groups derived from tetrahydrofuran, furan, thiophene, pyrrolidine, piperidine, pyridine, pyrrole, methylpyridine, and o-pyranone.

[0031] The alkyl, alkenyl, alicyclic, and heterocyclic groups can be unsubstituted or substituted with, for example, aryl, heteroaryl, C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkoxy, amino, carboxyl, halogen, nitro, cyano, -SOH, phosphonyl, or hydroxyl groups. When the alkyl, alkenyl, alicyclic, or heterocyclic groups are substituted, the substituents are preferably C1-C4 alkyl, halogen, nitro, amide, hydroxyl, carboxyl, sulfonyl, or phosphonyl.

[0032] The term "aryl" includes aromatic hydrocarbon groups, including fused aromatic rings such as phenyl and naphthyl.

[0033] The term "heteroaryl" includes heterocyclic aromatic derivatives having at least one heteroatom (such as nitrogen, oxygen, phosphorus, or sulfur), including, for example, furanyl, pyrroleyl, thiopheneyl, oxazolyl, pyridinyl, imidazolyl, thiazolyl, isoxazolylpyrazolyl, and isothiazolyl.

[0034] The term "heteroaryl" also includes at least one fused ring that is an aromatic ring, such as indolyl, purinyl, and benzofuranyl.

[0035] The aryl and heteroaryl groups can be unsubstituted on the ring or substituted with, for example, aryl, heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxyl, halogen, nitro, cyano, -SOH, phosphonyl, or hydroxyl groups. When the aryl, aralkyl, or heteroaryl group is substituted, the substituent is preferably a C1-C4 alkyl, halogen, nitro, amide, hydroxyl, carboxyl, sulfonyl, or phosphonyl group.

[0036] When substituents are described in their conventional chemical formulas, they are written from left to right. They also include chemically identical substituents that would result from writing the structure from right to left. For example, -CH2O- is equivalent to -OCH2-.

[0037] The terms “optional” or “optionally” refer to events or circumstances described below that may or may not occur, and the description includes instances where the events or circumstances occur and instances where they do not occur.

[0038] According to one embodiment, the polyetheramine salt of the fuel additive composition can be obtained by: (a) mixing a polyoxyethylene monoamine with at least one of dicarboxylic acid or tricarboxylic acid; or (b) mixing a polyoxyethylene polyamine with at least one of monocarboxylic acid, dicarboxylic acid or tricarboxylic acid.

[0039] In one embodiment, the polyoxyalkylene monoamine is a compound containing an amino group attached to the end of a polyether backbone. This amino group can be a primary amino group (-NH₂) or a secondary amino group (-NH₃). In one embodiment, the amino group is a primary amino group. As further discussed below, the polyether backbone is based on, i.e., as further defined by the alkylene oxide group, such as propylene oxide (PO), ethylene oxide (EO), butane oxide (BO), and mixtures thereof. In the mixed structure, the proportions can be any desired proportions and can be block (e.g., repeating or alternating) arrangements or random distributions. In a non-limiting example, in a mixed EO / PO structure, the EO:PO ratio can be from about 1:1 to about 1:50, and vice versa. Thus, the polyoxyalkylene monoamine can substantially define polyethylene oxide, propylene oxide, and / or butene oxide. The molecular weight of the polyoxyalkylene monoamine can vary and can reach about 6,000.

[0040] Polyoxyalkylene monoamines are typically prepared by reacting a monoprotic initiator (e.g., an alcohol) with ethylene oxide and / or propylene oxide and / or butane oxide. Following this reaction, the resulting terminal hydroxyl groups are converted to amines, thereby providing a polyether backbone comprising propylene oxide (PO), ethylene oxide (EO), butane oxide (BO), or mixtures thereof, and a terminal amino group, such as a primary or secondary amino group, preferably a primary amino group. According to one embodiment, the alcohol may be an aliphatic alcohol having 1-35 carbon atoms or an aromatic alcohol having 6-35 carbon atoms, both of which may be further structurally substituted with substituents such as alkyl, aryl, aralkyl, and alkylaryl groups. In another embodiment, the alcohol is an alkanol having 1-18 carbon atoms or 1-10 carbon atoms, such as lower alkyl-derived alkanols, including, for example, methanol, ethanol, propanol, butanol, isopropanol, sec-butanol, etc. In another embodiment, the alcohol may be an alkylphenol, wherein the alkyl substituent is a straight-chain or branched alkyl group with 1-24 carbon atoms (such as 4-16 carbon atoms), or an aryl-substituted phenol, including monophenylphenol, diphenylphenol and triphenylphenol, or alkylarylphenol, or arylalkylphenol, such as tristyrylphenol, or naphthol, or alkyl-substituted naphthol.

[0041] According to a specific implementation, polyoxyethylene monoamine is a compound having the following general formula:

[0042]

[0043] Where Z is C1-C 40 Alkyl or C1-C 40 Alkylphenol group; each Z' is independently hydrogen, methyl, or ethyl; and e is an integer from about 1 to about 50. Specific examples include, but are not limited to, compounds having the following formula:

[0044] ;

[0045] ;

[0046] and

[0047]

[0048] Where Me is methyl, Et is ethyl; f is an integer from about 13 to about 14; e is an integer from about 2 to about 3. Such polyoxyalkylene monoamines included in the above formulas include JEFFAMINE® M-600, M-1000, M-2005, M-2070, FL-1000 (where f is 14 and Me or Et is methyl), C-300 (where e is about 2.5); XTJ-435 and XTJ-436 amines.

[0049] According to another embodiment, the polyoxyethylene polyamine is a polyoxyethylene diamine. Procedures for manufacturing polyoxyethylene diamines are described, for example, in U.S. Patent No. 3,654,370, the contents of which are incorporated herein by reference. In a specific embodiment, the polyoxyethylene diamine is an amine-terminated polyoxyethylene glycol. The polyether backbone of such polyoxyethylene glycol may comprise ethylene oxide, propylene oxide, butane oxide, or mixtures thereof, thus the polyoxyethylene primary diamine may have the following general formula:

[0050]

[0051] Where m is an integer from 2 to about 100, and each R2 is independently hydrogen, methyl, or ethyl. In some embodiments, each R2 is independently hydrogen or methyl, and m is an integer from 2 to about 70, or from 2 to about 35, or from 2 to about 7. In other embodiments, each R2 is independently hydrogen or methyl, and m is an integer from 6 to about 70, or from about 6 to about 35. In other embodiments, each R2 is methyl, and m is an integer from 2 to about 70. Examples of these compounds include JEFFAMINE® D-series amines available from Huntsman Petrochemical LLC, such as JEFFAMINE® D-230 amine, where R2 is methyl and m is about 2.6, and JEFFAMINE® D400 amine, where R2 is methyl and m is about 6.1, as well as similar compounds including polyoxyethylene primary diamines available from other companies.

[0052] In another embodiment, polyoxyethylene diamine has the following general formula:

[0053]

[0054] Where n and p are each independently an integer from about 1 to about 10, and o is an integer from about 2 to about 40. In some embodiments, o is an integer from about 2 to about 40, or from about 2 to about 13, or from about 2 to about 10. In another embodiment, o is an integer from about 9 to about 40, or from about 12 to about 40, or from about 15 to about 40, or even from about 25 to about 40. In other embodiments, n+p is an integer in the range of about 1 to about 6, or from about 1 to about 4, or from about 1 to about 3. Examples of these compounds include the JEFFAMINE® ED series amines available from Huntsman Petrochemical LLC, and similar compounds including polyoxyethylene primary diamines available from other companies.

[0055] In another embodiment, the polyoxyethylene diamine may have the following formula:

[0056]

[0057] Where g is an integer from about 2 to about 3. Examples of these compounds include the JEFFAMINE® EDR series of amines available from Huntsman Petrochemical LLC, and similar compounds including polyoxyethylene primary diamines available from other companies.

[0058] In another embodiment, the polyoxyethylene polyamine is a polyoxyethylene triamine. Polyoxyethylene triamines can also be based on ethylene oxide, propylene oxide, or butane oxide, and mixtures thereof, and can be prepared by reacting such oxides with a triol initiator (e.g., glycerol or trimethylolpropane) followed by amination of the terminal hydroxyl groups. In one embodiment, the polyoxyethylene triamine may have the following general formula:

[0059]

[0060] Each R3 is independently hydrogen, methyl, or ethyl, R4 is hydrogen, methyl, or ethyl, t is 0 or 1, and h, i, and j are independently integers from about 1 to about 100. In one embodiment, R4 is hydrogen or ethyl. In another embodiment, each R3 is independently hydrogen or methyl, and in some embodiments, each R3 is methyl. In yet another embodiment, h+i+j is an integer in the range of about 1 to about 100 or from about 5 to about 85. Examples of these compounds include JEFFAMINE® T-series amines available from Huntsman Petrochemical LLC, such as JEFFAMINE® T3000, where R3 is methyl, R4 is hydrogen, t is 0, and h+i+j is 50, as well as similar compounds including polyoxyethylene primary triamines provided by other companies.

[0061] The polyetheramine salts of the present invention can be prepared by mixing a polyoxyethylene monoamine or polyamine with a carboxylic acid under complete salting ratio and at ambient conditions or elevated temperatures using gentle stirring. The carboxylic acid can be a saturated or unsaturated carboxylic acid having a straight chain and / or branched chains. It can be natural or synthetic, and can be aliphatic or aromatic. Carboxylic acids include those having the formula R-(COOH). n Any compound wherein R can be hydrogen, alkyl, alkenyl, alicyclic, aryl, heteroaryl, or heterocyclic, and n is 1, 2, or 3.

[0062] In one embodiment, the carboxylic acid is a monocarboxylic acid. Preferably, the monocarboxylic acid has C1-C2. 24 Alkyl groups. Examples of monocarboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, isopropionic acid, butyric acid, valeric acid, isovaleric acid, neovaleric acid, hexanoic acid, isohexanoic acid, 2-ethylbutyric acid, heptanoic acid, 2-methylhexanoic acid, isohexanoic acid, neoheptanoic acid, octanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, isodecanic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, heptadecanic acid, glycolic acid, lactic acid, salicylic acid, acetylsalicylic acid, stearylmandelic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanic acid, erucic acid, benzanoic acid, and mixtures thereof.

[0063] According to another embodiment, the carboxylic acid is a dicarboxylic acid. Examples of dicarboxylic acids include, but are not limited to, maleic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, dimer acids produced by the polymerization of unsaturated fatty acids and generally containing an average of about 18 to about 44 carbon atoms, and mixtures thereof.

[0064] In yet another embodiment, the carboxylic acid is a tricarboxylic acid. Examples of tricarboxylic acids include, but are not limited to, trimellitic acid, citric acid, isocitric acid, and agaric acid, trimeric acids produced by the trimerization of unsaturated fatty acids and generally containing an average of about 18 to about 30 carbon atoms, and mixtures thereof.

[0065] In addition to the polyetheramine salts described above, the fuel additive composition may also include one or more additional performance additives. These additional performance additives may be based on several factors, such as the type of internal combustion engine and the type of hydrocarbon-containing composition used in the engine, the quality of the hydrocarbon-containing composition, and the operating conditions of the engine. Additional performance additives may include organic solvents, antioxidants (such as hindered phenols or their derivatives and / or diarylamines or their derivatives), various corrosion inhibitors (such as alkenyl succinic acids, including PIB succinic acid), and / or detergent / dispersant additives, such as Mannich base dispersants, including: reaction products of hydrocarbon-substituted phenols, aldehydes, and amines or ammonia; polyisobutylene amine; or glyoxylates.

[0066] Other additives may include: dyes, antibacterial and bactericidal agents, gum inhibitors, markers, and demulsifiers, such as polyalkoxylated alcohols. Other additives may include additional lubricants, such as fatty carboxylic acids, metal deactivators (such as aromatic triazoles or their derivatives), and valve seat shrinkage additives (such as alkali metal sulfosuccinates). Additional additives may include antistatic agents, de-icing agents, combustion modifiers (such as octane or hexadecane modifiers), and fluidizing agents (such as mineral oils and / or poly(α-olefins) and / or polyethers).

[0067] The polyetheramine salt may be present in the fuel additive composition in an amount of at least 0.5% by weight, or at least 1% by weight, or at least 10% by weight, or at least 20% by weight, or at least 30% by weight, or at least 40% by weight, or at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or even at least 99% by weight, based on the total weight of the fuel additive composition.

[0068] In another embodiment, one or more additional performance additives may be present in the fuel additive composition at less than 90% by weight, or less than 50% by weight, or less than 20% by weight, or less than 10% by weight, or less than 1% by weight, based on the total weight of the fuel additive composition.

[0069] Exemplary fuel additive compositions are shown in the table below:

[0070]

[0071] According to another embodiment, a packaging product is provided, comprising: a) a container having at least one outlet; and b) a fuel additive composition.

[0072] According to one embodiment, the packaging product of the present invention includes a container having a sealing device, such as a lid, cover, cap, or stopper for sealing the container. In another embodiment, the sealed container also has a nozzle or pouring spout. The sealed container may be cylindrical, elliptical, circular, rectangular, can, basin, square, or pot-shaped and contains the fuel additive composition of the present invention.

[0073] In yet another embodiment, the container may be made of any material, such as steel, glass, aluminum, cardboard, tinplate, plastics (including but not limited to high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), oriented polypropylene (OPP), polyethylene (PE), or polyamide), as well as mixtures, laminates, or other combinations thereof.

[0074] According to another embodiment, a fuel composition comprising a fuel additive composition and a hydrocarbon-containing composition is provided.

[0075] In other embodiments, the fuel additive composition may contain a polyetheramine salt in the fuel composition at an amount of at least 10 ppm, 12 ppm, 25 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, or 300 ppm based on the total weight of the fuel composition. In other embodiments, the fuel additive may contain a polyetheramine salt in the fuel composition at an amount of less than 5000 ppm, 2500 ppm, 2000 ppm, 1500 ppm, 1000 ppm, 750 ppm, or 500 ppm based on the total weight of the fuel composition.

[0076] In another embodiment, the hydrocarbon-containing composition is liquid at room temperature and can be used to fuel an engine. The hydrocarbon-containing composition may be a petroleum distillate comprising gasoline as defined in ASTM D4814; in other embodiments, the hydrocarbon-containing composition is leaded or unleaded gasoline. The fuel composition may also contain oxygen-containing substances such as alcohols, ethers, ketones, carboxylic acid esters, nitroalkanes, or mixtures thereof. For example, the fuel composition may contain, for example, methanol, ethanol, butanol, methyl tert-butyl ether, or methyl ethyl ketone. In one embodiment, the fuel composition may contain 0.1 vol% to 100 vol% of an oxygen-containing substance based on the total volume of the fuel composition. In another embodiment, the fuel composition may contain 0.1 vol% to 100 vol% of a hydrocarbon-containing composition (e.g., gasoline) based on the total volume of the fuel composition. In another embodiment, the oxide may be ethanol. In other embodiments, the fuel composition may contain gasoline and 5 vol% to 30 vol% of ethanol based on the total volume of the fuel composition.

[0077] A fuel composition can be prepared by combining the hydrocarbon composition, a fuel additive composition, and an oxygen-containing compound before the hydrocarbon composition is placed in a vehicle. For example, the fuel additive composition can be added and mixed with the hydrocarbon composition such that the polyetheramine salt is present at a concentration of at least 10 ppm, or at least 20 ppm, or at least 50 ppm, or at least 100 ppm based on the total weight of the fuel composition. The added fuel composition can then be pumped into the fuel tank. In other embodiments, the fuel composition can be added to the vehicle's fuel tank, and the fuel additive composition containing the polyetheramine salt can be added to a separate dosing tank in the vehicle, and then metered into the fuel composition at a concentration of at least 10 ppm while the vehicle is in operation. This is referred to as "on-board dosing".

[0078] In one embodiment, the above-described fuel composition is useful for liquid-fuel engines and / or spark-ignition engines, and may include engines for hybrid vehicles and stationary engines. The type of engine is not overly limited, and includes, but is not limited to, V-type, inline, opposed, and rotary engines. The engine may be a naturally aspirated, boost-charged, electronically boost-charged, turbocharged, or turbocharged engine. The engine may be a carburetor or fuel-injected gasoline engine. Therefore, the engine may have a carburetor or fuel injectors (including piezoelectric injectors).

[0079] In one embodiment, the engine may be a gasoline direct injection (“GDI”) engine (injector or wall-guided, or a combination thereof), a port fuel injection (“PFI”) engine, a homogeneous charge compression ignition (“HCCI”) engine, a stoichiometric combustion or lean-burn engine, a spark controlled compression ignition (“SPCCI”) engine, a variable compression, Miller cycle, or Atkinson cycle engine, or a combination thereof, such as an engine that incorporates both GDI and PFI injectors in the same engine. Suitable GDI / PFI engines include two-stroke or four-stroke engines that use gasoline, a gasoline / ethanol blend, or any of the fuel compositions described in the foregoing section as fuel. The fuel composition may reduce corrosion, wear, and / or improve fuel economy of the engine (such as a GDI or GDI / PFI engine). In other embodiments, the fuel composition may be prepared using an on-board dispensing system for use with GDI engines, PFI engines, or combinations thereof.

[0080] In other embodiments, any of the aforementioned engines may be equipped with a catalyst or device for treating exhaust emissions (such as reducing NOx). In other embodiments, the engine may be a multi-fuel engine capable of operating with more than one type of fuel (typically gasoline and ethanol or gasoline and methanol). In other embodiments, any of the aforementioned engine types may be present in a hybrid electric vehicle, which also includes an electric motor.

[0081] Therefore, in another embodiment, a method is provided for preventing corrosion and reducing wear on metal, plastic, or synthetic parts or surfaces of fuel system components or internal combustion engines, the method comprising combining an effective amount of a fuel additive composition with a hydrocarbon-containing composition to form a fuel composition, and bringing the metal, plastic, or synthetic part or surface into contact with the fuel composition during engine operation.

[0082] Generally, fuel additive compositions can be added in small amounts (i.e., the amount that effectively provides corrosion reduction and friction reduction to gasoline) to hydrocarbon-containing compositions or gasoline. The effective amount of the fuel additive composition can be about 0.0002-0.2% by weight based on the total weight of gasoline. In some embodiments, an amount of about 0.001-0.01% by weight based on the total weight of gasoline is preferred, the latter corresponding to about 3 and 30 PTB (pounds of additive per 1000 barrels of hydrocarbon fuel or gasoline), respectively.

[0083] In another embodiment, a method is provided for preventing corrosion and reducing wear on metal, plastic, or synthetic parts or surfaces of fuel system components or internal combustion engines by combining an effective amount of a fuel additive composition with a hydrocarbon-containing composition to form a fuel composition, and bringing the metal, plastic, or synthetic parts or surfaces into contact with the fuel composition during engine operation.

[0084] It is well known that certain fuel additives can reach the lubricating oil film coated on the cylinder wall before combustion and can accumulate in the engine oil over time. Therefore, it is contemplated that in one embodiment, the polyetheramine salt of the fuel additive composition accumulates in the engine oil. Thus, in one embodiment, the present invention provides an oil composition comprising engine oil and a polyetheramine salt of a fuel additive composition as defined herein.

[0085] The invention will now be further described with reference to the following non-limiting examples.

[0086] Example

[0087] The friction reduction of the fuel additive composition of the present invention in gasoline was tested using a high-frequency reciprocating rig (HFRR). The HFRR was manufactured by the PCS Group. The gasoline was purchased from Haltermann Solutions (HF0437, Tier II EEE). The liquid loading volume was approximately 15 mL. The HFRR test in gasoline was conducted under the following conditions.

[0088] Duration 75 minutes

[0089] Temperature 25°C

[0090] 50Hz

[0091] Stroke 1mm

[0092] Loading 200g

[0093] Sample steel AISI E-52100

[0094] To determine corrosion inhibition performance, a carbon steel sample block was sanded before use, and then half of the sample block was immersed in the liquid fuel composition and kept at a temperature of about 30°C for 5 hours with stirring, as further described below.

[0095] Synthesis of fuel additive compositions

[0096] Mix polyoxyalkylene monoamines or polyoxyalkylene polyamines with carboxylic acids at ambient temperature at an amine-to-acid ratio of approximately 1:1 for 60 minutes. Carboxylic acids include oleic acid, isostearic acid, and dimer acids. Polyoxyalkylene monoamines and polyoxyalkylene polyamines include JEFFAMINE® C-300, M-600, FL-1000, D-230, D-400, and T-3000 amines. The composition of the fuel additive is summarized in the table below.

[0097]

[0098] The fuel additive composition in gasoline at a salt content level of 0.15% (1500 ppm) was evaluated using HFRR.

[0099] Examples 1 and 2 were blended with additive-free gasoline (HF0437) at a polyetheramine salt dosage level of 1500 ppm. The wear marks of each example were measured according to ASTM D6709, and the results are as follows.

[0100]

[0101] Fuel additive compositions with a salt content level of 0.30% (300 ppm) in gasoline were evaluated using HFRR.

[0102] Examples 1, 3, 4, 5, 6, and 8 were horizontally blended with additive-free gasoline (HF0437) at a concentration of 300 ppm of polyetheramine salt. The wear marks of each example were measured, and the results are as follows.

[0103]

[0104] Fuel additive compositions with a salt content level of 0.15% (150 ppm) in gasoline were evaluated using HFRR.

[0105] Examples 1, 3, 4, 5, 6, and 7 were horizontally blended with additive-free gasoline (HF0437) at a concentration of 150 ppm of polyetheramine salt. The wear marks of each example were measured, and the results are as follows.

[0106]

[0107] As demonstrated above, the fuel additive compositions according to the present invention can significantly reduce wear even at very low polyetheramine salt dosage levels.

[0108] The rust-preventive properties of the fuel additive composition in a gasoline / salt water mixture at a salt concentration level of 0.10% (100 ppm) were evaluated. 150 g of HF0437 was mixed with 15 g of seawater, followed by the addition of the examples shown in the table below. To determine the corrosion inhibition performance, a carbon steel sample block was sanded before use, and half of the metal sample block was then immersed in the liquid fuel additive and kept at approximately 30°C for 5 hours with stirring.

[0109]

[0110] Fuel additive composition. C1 and C2 are a mixture of polyoxyethylene monoamine and monocarboxylic acid.

[0111] Based on the results, the fuel additive composition according to the invention provides rust prevention properties in gasoline / seawater mixtures, and in particular, the fuel additive composition of the invention provides significantly better rust prevention properties than comparative fuel additive compositions C1 and C2.

[0112] Although various embodiments of making and using the invention have been described in detail above, it should be understood that the invention provides many applicable inventive concepts that can be embodied in a variety of specific situations. The specific embodiments discussed herein only illustrate specific methods of making and using the invention and do not limit the scope of the invention.

Claims

1. A fuel additive composition for reducing corrosion and increasing lubricity of hydrocarbon-containing compositions in contact with components of a fuel system or an internal combustion engine, said fuel additive composition comprising a polyetheramine salt obtained by mixing a polyoxyethylene monoamine with a carboxylic acid at a ratio of amine number to acid number of 1:

1. The carboxylic acid mentioned above includes those having the formula R-(COOH). n Any compound wherein R is hydrogen, alkyl, alkenyl, alicyclic, aryl, heteroaryl, or heterocyclic, and n is 1, 2, or 3. The polyoxyethylene monoamine mentioned above is a compound having the following general formula: Where Z is C1-C 40 Alkylphenol group; each Z' is independently hydrogen, methyl or ethyl; and e is an integer from 1 to 50.

2. The fuel additive composition according to claim 1, wherein the carboxylic acid is selected from the following monocarboxylic acids: formic acid, acetic acid, propionic acid, isopropionic acid, butyric acid, valeric acid, isovaleric acid, neovaleric acid, hexanoic acid, isohexanoic acid, 2-ethylbutyric acid, heptanoic acid, 2-methylhexanoic acid, isohexanoic acid, neoheptanoic acid, octanoic acid, isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, isodecanic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, heptadecanic acid, glycolic acid, lactic acid, salicylic acid, acetylsalicylic acid, stearylmandelic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanic acid, erucic acid, benzanoic acid, and mixtures thereof.

3. The fuel additive composition according to claim 1, wherein the carboxylic acid is a dicarboxylic acid selected from the following: maleic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid and terephthalic acid, dimer acids and mixtures thereof.

4. The fuel additive composition according to claim 1, wherein the polyetheramine salt is obtained by mixing polyoxyethylene monoamine with dicarboxylic acid.

5. The fuel additive composition according to claim 1, further comprising one or more performance additives.

6. A fuel composition comprising the fuel additive composition and the hydrocarbon-containing composition according to any one of claims 1-5.

7. The fuel composition according to claim 6, wherein the hydrocarbon-containing composition comprises gasoline.

8. The fuel composition according to claim 7, further comprising an oxygen-containing component.

9. The fuel composition of claim 8, wherein the oxygen-containing component comprises ethanol.

10. The fuel composition of claim 9, wherein the fuel composition comprises 5-30% by volume of ethanol based on the total volume of the fuel composition.

11. A method for preventing corrosion and reducing wear on metal, plastic or synthetic parts or surfaces of fuel system components or internal combustion engines, the method comprising combining an effective amount of a fuel additive composition as defined in any one of claims 1-5 with a hydrocarbon-containing composition to form a fuel composition, and contacting the metal, plastic or synthetic parts or surfaces with the fuel composition during engine operation.

12. The method according to claim 11, wherein the internal combustion engine is a gasoline direct injection engine.

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