Improvements in marine fuels

Abstract

To provide an additive composition for a marine fuel or a heating oil.SOLUTION: An additive composition for a marine fuel or a heating oil comprises a stabilised colloidal dispersion of catalytic metal particles, a neutral or overbased alkaline earth metal detergent and a carrier fluid miscible with a marine fuel oil, a heavy fuel oil, a marine distillate fuel and / or a residual fuel oil. Also provided are marine fuel compositions and heating oils compositions having the additive composition described above and associated methods and uses.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to additives for marine fuels for improving fuel efficiency, combustion characteristics, and / or emission performance of marine fuels, and more particularly to additives comprising a combination of an overbasic alkaline earth metal cleaning agent (wherein the alkaline earth metal is selected from calcium and / or strontium) and a colloidally dispersed and stabilized compound of iron and / or cerium. [Background technology]

[0002] Marine fuels constitute a portion of highly viscous and dense fuels available for combustion, and as a result of the refining process, they generally contain high levels of sulfur, asphaltenes, and other contaminants such as metal and catalytic particulate matter (CAT-fine). Therefore, they are sometimes considered inferior fuels undesirable for use in many modes of transport. However, in shipping and other industries, the size and robustness of typical marine engines make these fuels effectively usable. Thus, while the size of marine engines offers this advantage, burning large quantities of such fuels commensurate with their engine size results in high emissions of particulate matter and other pollutants that can impact coastal air quality, and fuel can account for 50-60% of a vessel's total operating costs. A similar consideration applies to kerosene.

[0003] The IMO (International Maritime Organization) implemented the 2020 Marine Fuel Oil Sulfur Cap (2020 sulfur cap) to address some emissions from marine engines by limiting sulfur levels in marine fuels to 0.5%. Further legislation specifically for marine engines, focusing on reducing NOx and greenhouse gas (GHG) emissions, is expected. For example, the IMO has set an ambitious target of reducing GHG emissions from the shipping industry by 70% by 2050 (compared to 2008 levels), and may require addressing challenges related to particulate matter emissions and coastal air quality in the future. Technological alternative fuels used in automotive transport to address NOx and GHG emission concerns using batteries and renewable fuels are actually difficult to adopt in marine transport due to the size of marine engines, the relatively slow turnover rate of engine technology in the shipping industry (vessels typically have a lifespan of around 30 years or more), and especially the infrastructure supporting shipping related to refueling. While diesel and gasoline are used in combination with batteries and other renewable fuels in the automotive sector, the shipping industry is likely to continue to require large amounts of fossil fuels in the foreseeable future. Therefore, if the shipping industry is to achieve the GHG / emission targets set by the IMO, it is an important effort to pursue technologies that reduce fuel consumption and emissions from current ship fuels, in other words, technologies that promote more efficient ship operations by reducing GHG / NOx / sulfur emissions.

[0004] Marine fuel additives, such as catalytic metals, have been used with great enthusiasm to influence fuel combustion in order to improve performance. For example, Patent Document 1 describes combining metal compounds such as ferrocene with organic compounds and stabilizers to improve fuel efficiency by enabling the use of heavier and / or more polluted fuels instead of lighter and / or cleaner fuels. Patent Document 2 describes combining molecular-sized iron compounds such as ferrocene with overbasic magnesium compounds, the molecular size of which is achieved, for example, by dissolving the compounds in xylene. This combination has been shown to reduce diesel fuel consumption in automobiles and trucks by catalytic fuel additives, while simultaneously reducing pollutants from exhaust gases resulting from fuel combustion. Because catalytic fuel additives have low particle density and small particle size, there is little damage to the equipment using the additives, and the amount of metallic ash released into the atmosphere is considerably lower than the standards recommended by the Environmental Protection Agency at the time. Patent Document 3 describes soluble metallic fuel oil additives for inhibiting soot and / or particulate emissions during the combustion of oils. However, there is still a need for marine fuel additive compositions that can improve the fuel efficiency, combustion characteristics, and / or emissions performance of marine fuels, in particular, without changing the base fuel used. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2008084251 [Patent Document 2] U.S. Patent Application Publication No. 20150210947 [Patent Document 3] UK Patent Application Publication No. 2248068 [Overview of the project]

[0006] Surprisingly, it is now known that combinations of stabilized colloidal dispersions of catalytic metal compounds, particularly iron and / or cerium oxide / compounds, with alkaline earth metal cleaning agents containing calcium and / or strontium synergistically improve the fuel efficiency, emissions performance, and combustion characteristics of marine fuels and kerosene.

[0007] Accordingly, in a first aspect, the present invention comprises an additive composition for marine fuel or kerosene, comprising: (A) a colloidal dispersion of catalyst metal particles, wherein the particles comprise: i. a nucleus of a metal compound comprising at least one of iron, ruthenium, osmium, cerium, nickel, palladium, and platinum; ii. a colloidal dispersion comprising a polyalkenyl-substituted carboxylic acid or an anhydride, or a derivative thereof; (B) a neutral or overbasic alkaline earth metal cleaning agent comprising calcium and / or strontium; and (C) a carrier fluid miscible with marine fuel oil, heavy fuel oil, marine distilled fuel, and / or residual fuel oil.

[0008] In a second aspect, the present invention includes a marine fuel composition or kerosene composition comprising an additive composition according to the first aspect of the present invention, marine fuel oil, heavy fuel oil, marine distilled fuel, and / or residual fuel oil.

[0009] In a third aspect, the present invention includes a method for improving the fuel efficiency, combustion characteristics, and / or emission performance of a marine fuel or kerosene, the method comprising the step of combining the marine fuel or kerosene with an additive composition according to the first aspect of the present invention.

[0010] In a fourth aspect, the present invention includes a method for producing a marine fuel composition or a kerosene composition, the method comprising the step of combining marine fuel oil, heavy fuel oil, marine distilled fuel, and / or residual fuel oil with an additive composition according to the first aspect of the present invention.

[0011] In a fifth aspect, the present invention includes the use of an additive composition according to the first aspect of the present invention for improving the fuel efficiency, combustion characteristics, and / or emission performance of marine fuel or kerosene.

[0012] In a sixth aspect, the present invention provides the use of an effective small amount of a binary additive combination in marine fuel or kerosene to improve the fuel efficiency, combustion characteristics, and / or emissions performance of the marine fuel or kerosene. The binary additive combination comprises: (A) a colloidal dispersion of catalyst metal particles, wherein the particles consist of: (i) a nucleus of a metal compound comprising at least one of iron, ruthenium, osmium, cerium, nickel, palladium, and platinum as defined and identified herein; (ii) a colloidal dispersion comprising a polyalkenyl-substituted carboxylic acid or anhydride or derivative thereof as defined and identified herein; and (B) a neutral or overbasic alkaline earth metal cleaning agent comprising calcium and / or strontium as defined and identified herein.

[0013] In some embodiments of the present invention, such as the second to fifth aspects, marine fuel, kerosene, heavy fuel oil, marine distilled fuel, and / or residual fuel oil are present in a majority amount (e.g., more than 50% by mass) relative to the total mass of the composition. In some embodiments, such as the second to fifth aspects of the present invention, the additive composition is present in small amounts (e.g., less than 50% by mass) relative to the total mass of the composition. In some embodiments, the additive composition of the first embodiment and the binary additive combination of the sixth embodiment include: (A) a colloidal dispersion of catalyst metal particles, wherein the metal particles include: (i) the nuclei of a metal compound comprising at least one of iron and cerium, preferably iron; (ii) a colloidal dispersion comprising a polyalkenyl-substituted carboxylic acid or anhydride or derivative thereof as defined and identified herein; and (B) a neutral or overbasic alkaline earth metal cleaning agent as defined and identified herein. In some embodiments, the additive composition of the first embodiment and the binary additive combination of the sixth embodiment include: (A) a colloidal dispersion of catalyst metal particles, wherein the metal particles include: (i) the nuclei of a metal compound comprising at least one of iron and cerium, preferably iron; (ii) a colloidal dispersion comprising a polyalkenyl-substituted carboxylic acid or anhydride or derivative thereof as defined and identified herein; and (B) a neutral or overbasic calcium detergent as defined and identified herein.

[0014] In some embodiments, the additive compositions and binary additive combinations as defined and identified herein each include: (A) a colloidal dispersion of catalytic metal particles, wherein the metal particles comprise: (i) a nucleus of a metal compound containing at least one of iron and cerium, preferably iron; (ii) a colloidal dispersion containing a polyisobutenyl-substituted succinic anhydride or succinic acid or a derivative thereof as defined and identified herein; (B) an overbased calcium detergent as defined and identified herein. In some embodiments, the neutral or overbased alkaline earth metal detergent containing calcium and / or strontium of the (c) additive composition includes an overbased alkaline earth metal detergent such as the overbased calcium detergent as defined and identified herein. In some embodiments, the neutral or overbased alkaline earth metal detergent containing calcium and / or strontium of the (c) additive composition includes an overbased calcium salicylate detergent. In some embodiments, the present invention is directed to marine fuel oil, heavy fuel oil, marine distillate fuel, and / or residual fuel oil, particularly marine fuel or marine distillate fuel. In some embodiments, the additive compositions and binary additive combinations as defined and identified herein each include (A) a colloidal dispersion of catalytic metal particles, wherein the metal particles comprise (i) an iron compound nucleus. In some embodiments, the present invention aims to improve the combustion characteristics of marine fuel or marine distillate fuel. In some embodiments, the present invention aims to reduce emissions from marine fuel or marine distillate fuel. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] [Figure 1] Schematic diagram of a fuel system for introducing an additive(s) into the fuel of a Caterpillar MaK 6M20, 6-cylinder, 4-stroke test engine that performs pump-line-nozzle injection. [Figure 2]This is a thermogravimetric analysis (TGA) plot showing the mass loss from very low-sulfur fuel oil (VLSFO, 0.5% S fuel) as a function of temperature rise. The compositions tested include: (Base Fuel 1) Untreated VLSFO; (Composition 1 of the Invention) VLSFO containing the additive composition of the Invention in which metal (a)(i) is iron; and (Composition 2 of the Invention) VLSFO containing the additive composition of the Invention in which metal (a)(i) is cerium. [Modes for carrying out the invention]

[0016] definition The following definitions are provided for illustrative purposes only, not to limit them. "Alkyl" refers to a monovalent hydrocarbon group that does not contain double or triple bonds and is arranged in a branched or linear chain. "Alkylene" refers to a divalent hydrocarbon group that does not contain double or triple bonds and is arranged in a branched or linear chain. "Alkenyl" refers to a monovalent hydrocarbon group having one or more double bonds and arranged in a branched or linear chain. "PIB" stands for polyisobutylene, and includes both ordinary or "conventional" polyisobutylene and highly reactive polyisobutylene (HRPIB).

[0017] The meaning of a group being a specific polymer (e.g., polypropylene, poly(ethylene-copropylene) or PIB) encompasses polymers primarily containing the respective monomer, along with negligible amounts of other substitutions and / or interruptions along the polymer chain. In other words, the meaning of a group being a polypropylene group does not require that the group consist of 100% propylene monomer without linking groups, substituents, impurities, or other substituents (e.g., alkylene or alkenylene substituents). Such impurities or other substituents may be present in relatively small amounts, as long as they do not affect the industrial performance of the additive compared to the same additive containing each polymer substituent in 100% purity. "Hydrocarbyl" refers to a group or radical containing carbon and hydrogen atoms, bonded to the rest of the molecule via the carbon atom. Hydrocarbyl may also contain heteroatoms, i.e., atoms other than carbon and hydrogen, as long as they do not alter the essential hydrocarbon properties and characteristics of the group.

[0018] Furthermore, the following words and expressions, when used, have the following meanings: "Active ingredient" or "(ai)" means an additive material that is not a diluent or solvent. Unless otherwise indicated, all mass percentage values ​​stated herein mean mass percentages based on the active ingredient of each component; "Contains" or its synonyms specify the presence of the described feature, process, integer, or component, but does not exclude the presence or addition of one or more other features, processes, integers, components, or groups thereof; the expressions "consist of," "essentially consisting of," or their synonyms may be encompassed by "contains" or its synonyms, where "essentially consisting of" may include substances that do not materially affect the properties of the composition in question; "Main amount" means 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more of the composition; "Small amount" means less than 50% by mass of the composition, preferably less than 40% by mass, more preferably less than 30% by mass, and even more preferably less than 20% by mass; "An effective small amount" means a small amount sufficient to achieve the desired technical effect; "ppm" refers to a mass percentage of the active ingredient, meaning one part per million. "TBN" refers to the total base number measured according to ASTM D2896.

[0019] Furthermore, when used in this specification: The "calcium content" was measured according to ASTM 4951; "Phosphorus content" was measured according to ASTM D5185; The "sulfate ash content" was measured according to ASTM D874; The "sulfur content" was measured according to ASTM D2622; "KV100" refers to the kinematic viscosity at 100°C, measured according to ASTM D445.

[0020] "Particle size" refers to the particle size (φ) measured, for example, with a transmission electron microscope, where 80% of the particles have a diameter less than the indicated value. 80 This means ). In addition to other techniques known to those skilled in the art, a transmission electron microscope may be used by diluting the sample with xylene to a concentration of 0.035% by mass and filtering it through a carbon-supported grid. Typically, about 80–90% of particles can be correctly identified and measured from 2–5 transmission electron microscope images. It is also understood that various essential, optimal, and conventional components of use may be reacted under formulation, storage, or use conditions, and that the present invention also provides products obtainable as a result of any such reaction. Furthermore, it is understood that any of the upper and lower limits of quantity, range, and ratio described herein may be combined independently and include limits of the "approximate" quantity, range, or ratio of the subject.

[0021] Stabilized catalyst metal particles (A) Embodiments according to the present invention include a colloidal dispersion of catalyst metal particles and a polyalkenyl-substituted carboxylic acid or anhydride stabilizer. In the colloidal dispersion, the catalyst metal particles typically have a particle size of at least 1 nm, for example, with a lower limit independently ranging from 1 nm, 1.25 nm, 1.5 nm, 1.75 nm, 2 nm, 2.25 nm, 2.5 nm, 2.75 nm, 3 nm, 3.25 nm, 3.5 nm, 3.6 nm, 3.7 nm, 3.75 nm, 3.8 nm, 3.9 nm, 4 nm, 4.1 nm, 4.2 nm, 4.25 nm, 4.3 nm, 4.4 nm, 4.5 nm, 4.6 nm, 4.7 nm, 4.75 nm, 4.8 nm, 4.85 nm, 4.9 nm, 4.95 nm, or 5 nm. The grain size ranges independently and upper limit within the following ranges: 1 μm, 950 nm, 900 nm, 850 nm, 800 nm, 750 nm, 700 nm, 650 nm, 600 nm, 550 nm, 500 nm, 450 nm, 400 nm, 350 nm, 300 nm, 250 nm, 200 nm, 175 nm, 150 nm, 125 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 28 nm, 25 nm, 22 nm, 20 nm, 19 nm, 18 nm, 17 nm, 16 nm, or 15 nm. The grain size may also be 1 nm to 1 μm, 2 nm to 500 nm, 3 nm to 100 nm, 3 nm to 50 nm, or 5 nm to 15 nm.

[0022] catalytic metal compound The catalyst metal particles in this invention include metal compounds selected from iron, ruthenium, osmium, cerium, nickel, palladium, platinum, and mixtures thereof. The catalyst metal particles form colloidal dispersions in the additive composition and / or in marine fuel or marine fuel oil. That is, the metal compounds are not present in solution form, mainly or completely, as in the case of ferrocene. The catalyst metal particles may include one or more iron compounds, cerium compounds, and mixtures thereof (or the metal compounds may be those compounds and mixtures thereof). The anions in the compounds are not necessarily limited, but the catalyst metal particles may include oxides (or the metal compounds may be their oxides). The catalyst metal particles may include one or more iron oxides, cerium oxide, and mixtures thereof (or the metal compounds may be these oxides and mixtures thereof). The catalyst metal particles may include iron oxides such as iron(II) oxide, iron(III) oxide, and / or iron(II,III) oxides (or the metal compounds may be those iron oxides). The catalyst metal particles may contain iron(III) oxide and / or iron(II,III) oxide (or the metal compound may be those iron oxides).

[0023] Polyalkenyl-substituted carboxylic acid or anhydride stabilizer Additive component (A) comprises a polyalkenyl-substituted carboxylic acid or an anhydride stabilizer, or a derivative thereof. The stabilizer may be colloidally dispersible or soluble in marine fuel and / or marine fuel oil, as described herein. Alternatively, the stabilizer may be an organic compound having a hydrocarbyl chain and at least one (preferably two or more) carboxylic acid or carboxylate functional groups at the ends of the hydrocarbyl chain. When two or more carboxylic acid or carboxylate functional groups are present, it is preferable that these groups are separated from each other by three or fewer or two or fewer carbon atoms within the oil-soluble or oil-dispersible organic compound.

[0024] The polyalkenyl-substituted carboxylic acid or anhydride stabilizer may be a monocarboxylic acid or a polycarboxylic acid, preferably a mono-, di-, or tri-carboxylic acid, and more preferably a dicarboxylic acid. Therefore, in some embodiments, the polyalkenyl-substituted carboxylic acid or anhydride stabilizer has multiple carboxylic acid or carboxylic acid moieties. In some non-limiting examples of the aforementioned derivatives, any or all of the present carboxylic acid moieties are -(COO-) n M n+ It may be ionized in the form of the following: where M is an n-valent positively charged metal cation (e.g., a monovalent, divalent, or trivalent positively charged metal cation (i.e., n=1, 2, or 3)) or a quaternary ammonium cation. In examples where the polyalkenyl-substituted carboxylic acid or anhydride stabilizer is di-, tri-, or polycarboxylic acid, the carboxylic acid or carboxylate groups are preferably separated from each other by three or fewer or two carbon atoms within the polyalkenyl-substituted carboxylic acid or anhydride stabilizer. That is, each carboxylic acid or carboxylic acid moiety has at least one other carboxylic acid or carboxylic acid moiety separated from each carboxylic acid or carboxylic acid moiety by three or fewer or two carbon atoms within the polyalkenyl-substituted carboxylic acid or anhydride stabilizer. Thus, the carboxylic acid or carboxylic acid moieties may effectively form pairs or groups within the molecule, and each pair or group may preferably be separated from each other by three or fewer or two carbon atoms within the polyalkenyl-substituted carboxylic acid or anhydride stabilizer, or by more than four, five, six, seven, eight, nine, ten, or more than ten carbon atoms. Anhydrous automatically satisfies this definition, but multiple anhydrous moieties may be present, and the anhydrous groups may preferably be separated from each other by three or fewer carbon atoms, or by more than 10 carbon atoms, such as four, five, six, seven, eight, nine, ten, or more than ten carbon atoms, within a polyalkenyl-substituted carboxylic acid or anhydrous stabilizer. In some preferred embodiments where multiple carboxylic acids or carboxylic acid moieties are present within the polyalkenyl-substituted carboxylic acid or anhydride stabilizer, all carboxylic acids or carboxylic acid moieties are continuous. Continuous means that the separation of adjacent carboxylic acids or carboxylic acid moieties is due to three or fewer carbon atoms, or two or fewer carbon atoms, within the polyalkenyl-substituted carboxylic acid or anhydride stabilizer. Therefore, a continuous chain of separations by two or fewer carbon atoms within the polyalkenyl-substituted carboxylic acid or anhydride stabilizer can be said to connect all carboxylic acids or carboxylic acid moieties within the polyalkenyl-substituted carboxylic acid or anhydride stabilizer.

[0025] An exemplary anhydrous can also be represented by the following general formula: [ka] In the formula, R 1 C8-C 100 This represents a branched or linear polyalkenyl group. In some embodiments, the polyalkenyl group has 8 to 400 carbon atoms, for example, 12 to 100. The number-average molecular weight of the polyalkenyl moiety may be 200 to 10000, preferably 350 to 2000, and preferably 500 to 1000. Some examples of the number-average molecular weight of the polyalkenyl moiety include 100 to 4000, 200 to 2250, 250 to 2000, 500 to 1500, 750 to 1250, or 850 to 1100.

[0026] Suitable hydrocarbons or polymers used in the formation of the anhydride used in the present invention to generate the polyalkenyl moiety include homopolymers, interpolymers, or low molecular weight hydrocarbons. One family of such polymers is ethylene and / or H2C=CHR 1 Having at least one type of C3-C 28 It contains alpha-olefin polymers. In the formula, R 1is a linear or branched alkyl radical having 1 to 26 carbon atoms, wherein the polymer contains carbon-carbon unsaturation, preferably higher-order terminal ethylidene unsaturation. Preferably, such a polymer comprises an interpolymer of ethylene and at least one α-olefin of the above formula. In the formula, R 1 is alkyl having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 2 carbon atoms. Accordingly, useful α-olefin monomers and comonomers include, for example, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, decene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, and mixtures thereof (e.g., a mixture of propylene and butene-1). Examples of such polymers include propylene homopolymers, butene-1 homopolymers, ethylene-propylene copolymers, ethylene-butene-1 copolymers, and propylene-butene copolymers, wherein the polymer contains at least some terminal unsaturation and / or internal unsaturation. Preferred polymers are unsaturated copolymers of ethylene and propylene, and ethylene and butene-1. The interpolymer may contain a small amount, for example 0.5 to 5 mol%, of a C4-C 18 non-conjugated diolefin comonomer. However, it is preferred that the polymer contains only α-olefin homopolymers, interpolymers of α-olefin comonomers, and interpolymers of ethylene and α-olefin comonomers. The molar content of ethylene in the polymer employed is preferably in the range of 0% to 80%, more preferably 0% to 60%. When propylene and / or butene-1 is employed as a comonomer (s) with ethylene, the ethylene content of such a copolymer is most preferably 15 to 50%, but the ethylene content may be higher or lower than this.

[0027] These polymers are prepared in the presence of a catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound, from an α-olefin monomer, or a mixture of α-olefin monomers, or ethylene and at least one C3-C28 The polymer may also be prepared by polymerizing a mixture containing an α-olefin monomer. Using this method, a polymer can be provided in which 95% or more of the polymer chains have terminal etenylidene type unsaturation. The percentage of polymer chains exhibiting terminal etenylidene type unsaturation can be determined by Fourier transform infrared (FTIR) spectroscopy, titration, or C 13 It may also be measured by NMR. This latter type of interpolymer is given by formula POLY-C(R 1 )=CH2 is sometimes a characteristic feature. In the formula, R 1 C1-C 26 Preferably C1-C 18 , more preferably C1-C8, most preferably C1-C2 alkyl (e.g., methyl or ethyl), and POLY represents the polymer chain. 1 The alkyl group chain length varies depending on the comonomer(s) selected for polymerization. Small polymer chains may contain terminal ethenyl, i.e., vinyl, unsaturated moieties, i.e., POLY-CH=CH2, and some polymers may contain internal monounsaturated moieties, such as POLY-CH=CH(R 1 It is possible to include ) in the formula. 1 These are defined above. These terminally unsaturated interpolymers may be prepared by known metallocene chemistry, or as described in U.S. Patents No. 5,498,809; No. 5,663,130; No. 5,705,577; No. 5,814,715; No. 6,022,929; and No. 6,030,930.

[0028] Another useful class of polymers is the class of polymers prepared by cationic polymerization of isobutene and styrene. A common polymer in this class is polyisobutene, obtained by polymerization of a C4 purified stream with a butene content of 35-75% by mass and an isobutene content of 30-60% by mass in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. Preferred sources of monomers for producing poly-n-butene are petroleum feed streams such as raffinate II. These feed oils are disclosed in the art, such as U.S. Patent No. 4,952,739. Polyisobutylene is the most preferred backbone because it is readily available by cationic polymerization from butene streams (e.g., using AlCl3 or BF3 catalysts). Such polyisobutylene generally contain a residual unsaturated moiety in the amount of one ethylenic double bond per polymer chain located along the chain. A preferred embodiment involves preparing a reactive isobutylene polymer having terminal vinylidene olefins using polyisobutylene prepared from a pure isobutylene stream or a raffinate I stream. Preferably, these polymers, called highly reactive polyisobutylenes (HR-PIBs), have a terminal vinylidene content of at least 65%, for example 70%, more preferably at least 80%, and even more preferably at least 85%. The preparation of such polymers is described, for example, in U.S. Patent No. 4,152,499. HR-PIBs are well known and are commercially available under the trademark names Glissopal® (BASF) and Ultravis® (BP-Amoco).

[0029] The polyisobutylene polymers that may be used are generally based on hydrocarbon chains of 400 to 3000 units. Methods for producing polyisobutylene are well known. Polyisobutylene can be functionalized by halogenation (e.g., chlorination), thermal "ene" reaction, or free radical grafting using a catalyst (e.g., peroxide), as described below. The hydrocarbon or polymer backbone may be functionalized with carboxylic acid anhydride-producing moieties in any order, either selectively at intercarbon unsaturated sites on the polymer or hydrocarbon chain, or randomly along the chain, using any of the three methods described above, or a combination thereof. Methods for reacting polymeric hydrocarbons with unsaturated carboxylic anhydrides, and for preparing derivatives from such compounds, are described in U.S. Patent Nos. 3,087,936; 3,172,892; 3,215,707; 3,231,587; 3,272,746; 3,275,554; 3,381,022; 3,442,808; 3,565,804; 3,912,764; 4,110,349; 4,234,435; 5,777,025; 5,891,953; and European Patent No. 0382 This is described in Specification 450; Canadian Patent No. 1,335,895; and British Patent Application Publication No. 1,440,219. Polymers or hydrocarbons may be functionalized at the carboxylic anhydride moiety by reacting the polymer or hydrocarbon under conditions in which a functional moiety or agent, i.e., an acid anhydride, is added to the polymer or hydrocarbon chain, mainly at the intercarbon unsaturated (also called ethylenically or olefinically unsaturated) moiety, using halogen-assisted functionalization (e.g., chlorination) or thermal "ene" reactions.

[0030] Selective functionalization can be achieved by halogenating, for example chlorinating or brominating, an unsaturated α-olefin polymer by passing chlorine or bromine through the polymer for 0.5 to 10 hours, preferably 1 to 7 hours, at a temperature of 60°C to 250°C, preferably 110°C to 160°C, for example 120°C to 140°C, so that the chlorine or bromine content is 1 to 8% by mass, preferably 3 to 7% by mass, relative to the mass of the polymer or hydrocarbon. Then, the halogenated polymer or hydrocarbon (hereinafter referred to as the skeleton) is reacted with a sufficient monounsaturated reactant, for example a monounsaturated carboxylic acid reactant, that can add the required number of functional groups to the skeleton, at 100°C to 250°C, usually 180°C to 235°C, for 0.5 to 10 hours, for example 3 to 8 hours. As a result, the obtained product will contain the desired number of moles of monounsaturated carboxylic acid reactant per mole of halogenated skeleton. Alternatively, the skeleton and the monounsaturated carboxylic acid reactant are mixed and heated while adding chlorine to a high-temperature material. Chlorination usually helps to increase the reactivity between the starting material, an olefin polymer, and the monounsaturated functionalized reactant. However, chlorination is not necessary for several polymers or hydrocarbons considered for use in the present invention, particularly those preferred polymers or hydrocarbons with high terminal bond content and reactivity. Therefore, it is preferable to bring the backbone and the monounsaturated functional reactant (carboxyl reactant) into contact at high temperature to induce the initial thermal "ene" reaction. The ene reaction is well known.

[0031] Hydrocarbons or polymer backbones can be functionalized by randomly attaching functional portions along polymer chains in various ways. For example, polymers may be grafted with monounsaturated carboxylic acid reactants in solution or solid form in the presence of a free radical initiator, as described above. When carried out in solution, grafting is performed at high temperatures in the range of 100°C to 260°C, preferably 120°C to 240°C. Free radical-initiated grafting is preferably achieved in a mineral lubricating oil solution containing, for example, 1 to 50% by mass, preferably 5 to 30% by mass, of the polymer relative to the initial total lubricating oil solution. The free radical initiators that may be used are peroxides, hydroperoxides, and azo compounds, preferably those with a boiling point exceeding 100°C and that thermally decompose within the grafting temperature range to produce free radicals. Representative examples of these free radical initiators include azobutyronitrile, 2,5-dimethylhexa-3-ene-2,5-bis-tertiary butyl peroxide, and dicumene peroxide. When used, the initiator is usually used in an amount of 0.005 to 1% by mass relative to the mass of the reaction mixture solution. Typically, the mass ratio of the monounsaturated carboxylic acid reactant material to the free radical initiator is in the range of 1.0:1 to 30:1, preferably 3:1 to 6:1. Grafting is preferably carried out in an inert atmosphere, such as under nitrogen blanket treatment. The resulting grafted polymer is characterized by having carboxylic acid (or derivative) moieties randomly attached along the polymer chain, and it is understood that some parts of the polymer chain remain ungrafted. The free radical grafting described above can also be used for other polymers and hydrocarbons used in the present invention.

[0032] Preferred monounsaturated reactants used to functionalize the skeleton include mono and dicarboxylic acid materials, i.e., acid or acid derivative materials including: (i) monounsaturated C4-C 10 Dicarboxylic acids having (a) carboxyl groups in close proximity to each other (i.e., located on adjacent carbon atoms) and (b) at least one, preferably both, adjacent carbon atoms being part of a monounsaturated moiety; (ii) derivatives of (i), such as mono or diester derived from the anhydride or C1-C5 alcohol of (i); (iii) monounsaturated C3-C5 double bonds conjugated to a carboxyl group. 10 Monocarboxylic acids, i.e., monounsaturated C3-C with the structure -C=C-CO-. 10 Monocarboxylic acids; and derivatives of (iv)(iii), such as mono or diesters derived from the C1-C5 alcohol of (iii). Mixtures of monounsaturated carboxylic acid materials (i) to (iv) may also be used. Upon reaction with the skeleton, the monounsaturated portion of the monounsaturated carboxylic acid reactant becomes saturated. Thus, for example, maleic anhydride becomes skeleton-substituted succinic anhydride, and acrylic acid becomes skeleton-substituted propionic acid. Examples of such monounsaturated carboxylic acid reactants include fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and the aforementioned lower alkyl (e.g., C1-C4 alkyl) acid esters, such as methyl maleate, ethyl fumarate, and methyl fumarate. To provide the required functionalities, a monounsaturated carboxylic acid reactant, preferably maleic anhydride, is typically used in an equimolar amount of ~100% by mass, preferably in excess of 5 to 50% by mass, based on the moles of the polymer or hydrocarbon. Unreacted excess monounsaturated carboxylic acid reactant can be removed from the final dispersed product, for example, by stripping, usually under vacuum, if necessary.

[0033] Therefore, specific stabilizers include poly(isobutene)succinate anhydride (PIB-succinate anhydride) and poly(isobutene)succinate (PIB-succinate), more specifically poly(isobutene)succinate (PIB-succinate). If present, poly(isobutene)succinate anhydride and poly(isobutene)succinate may have any of the above-described characteristics of stabilizers, and may specifically, but not limited to, a polyisobutenyl moiety having 8 to 400 carbon atoms, for example 12 to 100, and / or a polyisobutenyl moiety having a number average molecular weight of 200 to 10000, preferably 350 to 2000, preferably 500 to 1000. Some examples of the number-average molecular weight of the polyisobutenyl moiety include 100-4000, 200-2250, 250-2000, 500-1500, 750-1250, or 850-1100. As can be seen from the following exemplary formula, PIB-succinic acid may be bismaleinated, where multiple succinic acid or anhydride derivatives are present in the polyalkenyl-substituted carboxylic acid or anhydride stabilizer (in particular, two are present), and these multiple succinic acid or anhydride derivatives may be separated from each other by three or fewer or two or fewer carbon atoms in the polyalkenyl-substituted carboxylic acid or anhydride stabilizer, or by more than four, five, six, seven, eight, nine, ten, or more than ten carbon atoms. Therefore, the multiple succinic acid or anhydride derivatives may consist of only one polyalkenyl substitution, as also shown in the following exemplary formula.

[0034] [ka] Poly(isobutene)succinic anhydride (PIB-succinic anhydride) and poly(isobutene)succinic acid (PIB-succinic anhydride) may be used in combination with catalyst metal particles (or metal compounds thereof) containing iron oxide, cerium oxide, and mixtures thereof, for example, catalyst metal particles (or metal compounds thereof) containing iron(II) oxide, iron(III) oxide and / or iron(II,III) oxide, or catalyst metal particles (or metal compounds thereof) containing iron(III) oxide and / or iron(II,III) oxide.

[0035] The stabilizer may be a fatty acid, and examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, caproleic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, brassic acid, nervonic acid, linoleic acid, dienoic acid, alpha-linolenic acid, alpha-linolenic acid, columbic acid, stearidonic acid, meadic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, and mixtures thereof. In some embodiments, the fatty acid or mixture thereof may include one or more polyunsaturated (two or more C=C double bonds), monounsaturated or saturated fatty acids, in particular, in addition to the corresponding di-, tri-, and poly-acids that become mono-, di-, or tri-carboxylic acids, it may also include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, caprolic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, brassic acid, nervonic acid, and mixtures and derivatives thereof, and thus may have any of the corresponding characteristics described above. The number of carbon atoms in the fatty acid may be at least 10, at least 12, at least 14, or at least 16, at most 30, at most 28, at most 26, or at most 24. The range of carbon atoms in fatty acids can be, for example, selected from 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30 at the lower limit, and selected from 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30 at the upper limit, such as 10-30, 12-28, 14-26, or 16-24. The stabilizer may be a natural fatty acid product such as a commercially available product, which is expected to contain a mixture of several, typically several, of the listed fatty acids.

[0036] Alkaline earth metal cleaning agent (B) Metal cleaning agents are additives based on metal salts of acidic organic compounds, so-called metal "soaps," and are sometimes called surfactants. Cleaning agents that may be used in fuels include oil-soluble neutral and overbasic salicylates, as well as sulfonates of metals, particularly alkali or alkaline earth metals, such as sodium, potassium, lithium, calcium, and magnesium, any of which may be present in the cleaning used in marine fuel or kerosene compositions according to any aspect of the present invention, with or without the presence of other alkali or alkaline earth metals. In the present invention, the metal cleaning agent includes calcium and / or strontium. Without intending to be bound by theory, it is considered that calcium and strontium, when considered as atoms in a non-excited state, may exhibit synergistic effects with the metal present in additive component (A) due to electronic effects, and that calcium and strontium are similar in that their lowest unoccupied electron orbitals are d orbitals. In beryllium and magnesium, the corresponding lowest unoccupied orbital is a p orbital, and in barium and radium, the corresponding lowest unoccupied orbital is an f orbital. In the specific cases of calcium and iron, the highest unoccupied orbital of calcium is the same as the highest occupied orbital of iron. Alkaline earth metal cleaning agent (B) may contain calcium (or the alkaline earth metal may be calcium).

[0037] Detergents may be used in combination, whether they are overbasic, neutral, or both. Detergents generally contain a polar tip with a long hydrophobic tail. Overbasic metal detergents usually contain a basic nucleus (e.g., a metal carbonate) stabilized by a surfactant shell that frequently forms micelles, and may be provided by reacting an excess amount of a metal base, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to produce a large amount of metal base. The degree to which the metal base reacts with the acidic gas is expressed as a percentage of the carbonation level (the value obtained by dividing the mass of the reacted excess metal base by the sum of the mass of the reacted excess metal base and the mass of the unreacted excess metal base). In the case of calcium hydroxide, for example, it is expressed as the value obtained by dividing the mass (or moles) of calcium present as Ca(OH)2 by the sum of the mass (or moles) of calcium as Ca(OH)2 and the mass (or moles) of calcium as CaCO3. Therefore, the degree of carbonation of the metal cleaner may be 50% to 95%, typically 60% to 90%, more typically 65% ​​to 90%, or 65% to 85%, and even more typically 70% to 80%. The degree of carbonation of the metal cleaner may be 85% or higher, for example, at least 86%, at least 87%, at least 90%, at least 91%, or at least 92%. The degree of carbonation is typically at most 100%, and at most 99%. The following general formula may be used to determine the degree of carbonation (DOC).

number

[0038] In the present invention, the metal cleaning agent may be a colloidal dispersion of cleaning agent particles, in which case the catalyst metal particles form a first colloidal dispersion and the metal cleaning agent particles form a second colloidal dispersion. In the colloidal dispersion, the particle size of the metal cleaning agent particles is typically at least 1 nm, for example, individually selected from 1 nm, 1.25 nm, 1.5 nm, 1.75 nm, 2 nm, 2.25 nm, 2.5 nm, 2.75 nm, 3 nm, 3.25 nm, 3.5 nm, 3.6 nm, 3.7 nm, 3.75 nm, 3.8 nm, 3.9 nm, 4 nm, 4.1 nm, 4.2 nm, 4.25 nm, 4.3 nm, 4.4 nm, 4.5 nm, 4.6 nm, 4.7 nm, 4.75 nm, 4.8 nm, 4.85 nm, 4.9 nm, 4.95 nm, or 5 nm. The range is as follows, with the upper limit being a range individually selected from 1 μm, 950 nm, 900 nm, 850 nm, 800 nm, 750 nm, 700 nm, 650 nm, 600 nm, 550 nm, 500 nm, 450 nm, 400 nm, 350 nm, 300 nm, 250 nm, 200 nm, 175 nm, 150 nm, 125 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 28 nm, 25 nm, 22 nm, 20 nm, 19 nm, 18 nm, 17 nm, 16 nm, or 15 nm. The particle size may also be 1 nm to 1 μm, 2 nm to 500 nm, 3 nm to 100 nm, 3 nm to 50 nm, or 5 nm to 15 nm. In the present invention, the metal cleaning agent (B) may be a hydrocarbyl-substituted hydroxybenzoate metal, more preferably a hydrocarbyl-substituted salicylate metal cleaning agent. Examples of metals include alkali metals (e.g., Li, Na, K) and / or alkaline earth metals (e.g., Mg, Ca), but include calcium and / or strontium, and preferably calcium. In some embodiments, the metal content of the detergent, which may be measured as alkali metal and / or alkaline earth metal content, or specific metal content of the detergent (e.g., lithium content, sodium content, potassium content, magnesium content, calcium content, and / or strontium content), may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 mass% to 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mass%, for example, 2 mass% to 15 mass%, 5 mass% to 12 mass%, 6 mass% to 10 mass%, or 7 mass% to 9 mass%. The metal, strontium, and / or calcium content of the detergent may be about 8 mass%. In some examples, the calcium content of metal cleaner (B) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14% to 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by mass, for example, 2% to 15% by mass, 5% to 12% by mass, 6% to 10% by mass, or 7% to 9% by mass, or about 8% by mass.

[0039] Examples of hydrocarbyls include alkyl and alkenyl compounds. A preferred hydrocarbyl-substituted hydroxybenzoate metal is alkyl-substituted calcium salicylate, which has the following structure: [ka] In the formula, R is a linear alkyl group. Multiple R groups may be bonded to the benzene ring. COO - The group can be positioned in the ortho, meta, or para position relative to the hydroxyl group; of these, the ortho position is preferred. The R group can be positioned in the ortho, meta, or para position relative to the hydroxyl group. Salicylic acid is usually prepared by carboxylation of phenoxide using the Kolbe-Schmitt method, in which case it is generally obtained in a miscible with uncarboxylated phenol (usually in a diluent). Salicylic acid may or may not be sulfurized, may be chemically modified, and / or may contain additional substituents. Methods for sulfurizing alkyl salicylic acid are well known to those skilled in the art and are described, for example, in U.S. Patent No. 2007 / 0027057. The number of carbon atoms in the alkyl group such as R in the above structure may be 8 to 100, preferably 8 to 24, for example, 14 to 20, or 14 to 18.

[0040] The sulfonates of the present invention may be prepared from sulfonic acids typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained from petroleum fractionation, or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives, such as chlorobenzene, chlorotoluene, and chloronaphthalene. Alkylation may be carried out in the presence of a catalyst using an alkylating agent having 3 to more than 70 carbon atoms. The number of carbon atoms in alkaryl sulfonic acid is usually 9 to 80 or more, preferably 16 to 60, per alkyl-substituted aromatic moiety. The oil-soluble sulfonates or alkaryl sulfonic acid may be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates, and ethers. The amount of metal compound is selected considering the desired TBN of the final product, but is usually in the range of 100 to 220% by mass (preferably at least 125% by mass) of the amount stoichiometrically required. The term "overbasic" is generally used to describe metal cleaning agents in which the ratio of the equivalent number of the metal portion to the equivalent number of the acid portion is greater than 1. The term "low basic" is used to describe metal cleaning agents in which the equivalent ratio of the metal portion to the acid portion is greater than 1 but about 2 or less.

[0041] "Overbasic calcium salt of surfactant" refers to an overbasic detergent in which the metal cation of the oil-insoluble metal salt is basically a calcium cation. Small amounts of other cations may be present in the oil-insoluble metal salt, but typically, at least 80 mol%, more typically at least 90 mol%, for example at least 95 mol%, of the cations in the oil-insoluble metal salt are calcium ions. Cations other than calcium may be obtained, for example, by using a surfactant salt in which the cation is a metal other than calcium in the production of the overbasic detergent. Preferably, the metal salt of the surfactant is also calcium. Carbonated overbasic metal cleaning agents typically contain amorphous nanoparticles. Furthermore, nanoparticle materials containing carbonates in the form of crystalline calcite and vaterite have been disclosed in the art. The basicity of a detergent may also be expressed in terms of total base number (TBN), sometimes referred to as base number (BN). Total base number is the amount of acid required to completely neutralize the basicity of an over-basic material. TBN may be measured using ASTM standard D2896 or an equivalent procedure. Detergents may have low TBN (i.e., TBN less than 50), medium TBN (i.e., TBN between 50 and 150), or high TBN (i.e., greater than 150, e.g., TBN between 150 and 500). Basicity may also be expressed as a basicity index (BI), which is the molar ratio of total base to total soap in an overbasic detergent, and in the context of the present invention, it may be in the range of 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, or 9.5 to 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10, for example, 0.1 to 10, 0.5 to 9, 1 to 8.5, 1.5 to 7, 2 to 5, or 2.5 to 3.5. The basicity index of the detergent may be approximately 3.

[0042] Additives used in combination The marine fuel oil of the present invention includes an additive combination which may (or may essentially) consist of additives (A) and (B). Accordingly, the treatment rate of the additive combination referred to herein is intended to be the treatment rate of the active components (A) and (B) in the marine fuel oil, but it should be understood that this additive combination may be introduced into the marine fuel oil in combination with, or simultaneously with, solvents, diluents, or other additives such as detergents, dispersants, stabilizers, demulsifiers, anti-emulsifiers, corrosion inhibitors, pour point depressants, and low-temperature fluidity improvers such as CFPP (low-temperature filter clogging point) modifiers, viscosity modifiers, lubricity improvers, or flammability improvers. Additional additives, such as those listed above, may be added or blended into the marine fuel oil additionally or alternatively, before or after combining additives (A) and (B), separately from, or simultaneously with, the additive combination referred to herein. The combined substances of (A) and (B) may, in principle, be used in any ratio suitable for the desired application. As a non-limiting example, the ratio may be a mass ratio based on the mass of the catalyst metal (e.g., iron and cerium from the other metals listed above) and the alkaline earth metal (calcium and strontium), and may be in the range of 1000:1 to 1:100, 100:1 to 1:10, 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, or 1:1 to 1:2 (or less than 1:1 to 1:2), for example, 1:1.1 to 1:2, 1:1.4 to 1:1.6, or about 1:1.5. Alternatively, the ratio may be the molar ratio of a catalyst metal (for example, iron and cerium from among the other metals listed above) to an alkaline earth metal (calcium and strontium), and may be in the range of 1000:1 to 1:1000, 100:1 to 1:100, 10:1 to 1:15, 5:1 to 1:10, 3:1 to 1:5, 2:1 to 1:4, 1:1 to 1:3 (or less than 1:1 to 1:3), 1:1.5 to 1:2.5, or 1:1.8 to 1:2.2, or approximately 1:2.

[0043] Carrier fluid The additive compositions according to the present invention typically further comprise a carrier fluid miscible with marine fuel oil. Suitable examples of such carrier fluids include kerosene, marine fuel oil (each described in further detail in the following sections), mineral oil, and hydrocarbon solvents. Suitable hydrocarbon solvents for colloids include commercially available mixed aromatic solvents such as Solvesso and Shellsol, as well as aliphatic solvents such as isoalkanes, including Isopar L. Other suitable solvents known in the art of additives may be used, for example, Norpar (pentane), Exxsol (de-aromatic hydrocarbon fluid), Nappar (naphthenic), Varsol (non-de-aromatic hydrocarbon fluid), xylene, and HAN 8080 (aromatic solvent).

[0044] marine fuel oil The additive of the present invention is intended for use in marine fuel or kerosene. Therefore, the present invention is intended to provide marine fuel and kerosene containing the additive according to the first aspect of the present invention. The marine fuel oil of the present invention may be defined in accordance with the marine fuel specifications for petroleum products of ISO 8217:2017, ISO 8217:2012, ISO 8217:2010, and / or ISO 8217:2005. It is understood that other regional specifications and / or supplier / operator specifications of other versions of ISO 8217 may be additionally or alternatively satisfied by marine fuels in accordance with the present invention. In some embodiments, the sulfur content of the oil may be reduced, for example, the sulfur content may be 0.5% by mass or less as sulfur atoms, for example, less than 0.5% by mass, 0.4% by mass or less, less than 0.4% by mass, 0.3% by mass or less, less than 0.3% by mass, 0.2% by mass or less, less than 0.2% by mass, 0.1% by mass or less, or less than 0.1% by mass. In some preferred embodiments, the sulfur content of the marine fuel oil may be less than 0.5% by mass as sulfur atoms, or even less than 0.1% by mass. In other embodiments, the sulfur content of the oil may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.75% by mass or less, or less than 0.5% by mass or less as sulfur atoms. For example, all or part of the ship fuel oil or kerosene of the present invention may be produced from crude oil by fractional distillation.

[0045] In the marine fuel oil or kerosene of the present invention, additives (A) and (B) may be used as one or more of the following: detergents, dispersants, stabilizers, demulsifiers, anti-emulsifiers, corrosion inhibitors, pour point depressants, and low-temperature fluidity enhancers such as CFPP modifiers, viscosity modifiers, lubricity enhancers, or flammability enhancers, or in combination therewith. Alternatively, an additive combination consisting of (A) and (B) may be used together with one or more additional additives such as detergents, dispersants, stabilizers, demulsifiers, anti-emulsifiers, corrosion inhibitors, low-temperature fluidity enhancers such as pour point depressants and CFPP modifiers, viscosity modifiers, lubricity enhancers, or flammability enhancers. (B) The TBN of the detergent (or each detergent) may be in the range of 0, 50, 100, or 150 for the lower limit and 300, 350, 400, 450, or 500 for the upper limit.

[0046] In principle, any ratio of (A) and (B) may be used in marine fuel or kerosene as long as it is suitable for the desired application. As a non-limiting example, the ratio may be a mass ratio based on the mass of the catalyst metal (e.g., iron and cerium, among the other metals listed above) to the mass of the alkaline earth metal (calcium and strontium), and the mass ratio may be in the range of 1000:1 to 1:100, 100:1 to 1:10, 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, or 1:1 to 1:2 (or less than 1:1 to 1:2), for example, 1:1.1 to 1:2, 1:1.4 to 1:1.6, or about 1:1.5. Alternatively, the ratio may be the molar ratio of catalyst metals (e.g., iron and cerium, among the other metals listed above) to alkaline earth metals (calcium and strontium), and the molar ratio may be in the range of 1000:1 to 1:1000, 100:1 to 1:100, 10:1 to 1:15, 5:1 to 1:10, 3:1 to 1:5, 2:1 to 1:4, 1:1 to 1:3 (or less than 1:1 to 1:3), 1:1.5 to 1:2.5, or 1:1.8 to 1:2.2, or about 1:2. The referenced amounts may include or exclude metals present in the fuel before the additive is added (e.g., metals in the base fuel) and / or metals added to the fuel from another source. The treatment rate of the additive composition of the present invention to marine fuel, marine fuel oil, or kerosene may be 1 ppm to 1000 ppm by mass of metal, for example, 5 ppm to 500 ppm, 10 ppm to 100 ppm, 25 ppm to 70 ppm, or 40 ppm to 60 ppm.

[0047] When iron is present, the treatment rate of the additive composition of the present invention (or colloidal dispersion of catalyst metal particles) to marine fuel, marine fuel oil, or kerosene may be 1 ppm to 1000 ppm by mass of iron, for example, 2 ppm to 500 ppm, 5 ppm to 200 ppm, 10 ppm to 100 ppm, 12 ppm to 50 ppm, or 15 ppm to 30 ppm. When calcium is present, the treatment rate of the additive composition of the present invention (or alkaline earth metal cleaning agent) to marine fuel, marine fuel oil, or kerosene may be 1 ppm to 1000 ppm by mass of calcium, for example, 2 ppm to 500 ppm, 5 ppm to 200 ppm, 10 ppm to 100 ppm, 15 ppm to 60 ppm, or 20 ppm to 40 ppm.

[0048] Methods and Uses The present invention also aims to provide a method for improving the fuel efficiency, combustion characteristics, and / or emission performance of marine fuel and / or kerosene, the method comprising the step of combining marine fuel and / or kerosene with an additive composition according to a first aspect of the present invention. The present invention also intends to provide a method for producing marine fuel and / or kerosene, the method comprising the step of combining marine fuel oil, heavy fuel oil, marine distilled fuel, and / or residual fuel oil with an additive composition according to a first aspect of the present invention. Furthermore, the present invention intends to use additive compositions according to a first aspect of the present invention for improving the fuel efficiency, combustion characteristics, and / or emission performance of marine fuels and / or kerosene, or for adding to marine fuels and / or kerosene. Additive compositions according to a first aspect of the present invention may also be used to process diesel fuel or other hydrocarbon fuels.

[0049] For example, the additive of the present invention reduces the fuel consumption of an engine that burns marine fuel (including heavy fuel oil and ultra-low sulfur fuel oil) and / or kerosene by more than 0.2%, or by 0.2%, more than 0.2%, 0.3%, more than 0.3%, 0.4%, more than 0.4%, 0.5%, more than 0.5%, 0.6%, more than 0.6%, 0.7%, more than 0.7%, 0.8%, more than 0.8%, 0.9%, more than 0.9%, and 1%. Alternatively, the reduction may be in the range from more than 1% to 5%, less than 5%, 4%, less than 4%, 3%, less than 3%, 2%, less than 2%, 1.5%, less than 1.5%, 1.4%, less than 1.4%, 1.3%, less than 1.3%, 1.2%, less than 1.2%, 1.1%, or less than 1.1%, for example, 0.2% to 2%, more than 0.3% to 1.5%, 0.5% to 1.5%, or 0.8% to 1.4%. As a further example, the additives of the present invention may reduce the total hydrocarbon emissions of engines burning marine fuels (including heavy fuel oils and ultra-low sulfur fuel oils) and / or kerosene by more than 3.6%, or by a range from more than 3.6%, 3.7%, more than 3.7%, 4%, more than 4%, 5%, more than 5%, 6%, more than 6%, 7%, more than 7%, 8%, or more than 8%, down to 20%, less than 20%, 17%, less than 17%, 15%, less than 15%, 14%, less than 14%, 13%, less than 13%, 12%, less than 12%, 11%, less than 11%, 10%, less than 10%, 9%, or less than 9%, for example, more than 3.6% to 20%, 3.7% to 18%, 5% to 15%, 7% to 12%, or 8% to 10%.

[0050] As a further example, the additives of the present invention may reduce nitric oxide emissions from engines burning marine fuels (including heavy fuel oils and very low sulfur fuel oils) and / or kerosene by more than 1.7%, or by a range from more than 1.7%, 2%, more than 2%, 3%, more than 3%, 4%, more than 4%, 5%, more than 5%, 6%, more than 6%, 6.5%, or more than 6.5%, down to 20%, less than 20%, 17%, less than 17%, 15%, less than 15%, 14%, less than 14%, 13%, less than 13%, 12%, less than 12%, 11%, less than 11%, 10%, less than 10%, 9%, less than 9%, 8%, less than 8%, 7%, or less than 7%, for example, more than 1.7% to 20%, 2% to 15%, 4% to 12%, 5% to 10%, or 6% to 8%. As a further example, the additives of the present invention reduce carbon monoxide emissions from engines burning marine fuels (including heavy fuel oil and ultra-low sulfur fuel oil) and / or kerosene by more than 0.4%, or by more than 0.4%, 0.5%, 0.5%, 1%, 1%, 1% or more, 1.5%, 1.5%, 2%, 2%, 2.5%, 2.5%, 3%, 3%, 3.5%, 3.5%, 4%, 4%, 4.5%, 4.5%, 5%, 5%, 5.5%, 5.5%, 6%, 6%, to 20%, less than 20%, 17%, less than 17%. The reduction may be in the range of 15%, less than 15%, 14%, less than 14%, 13%, less than 13%, 12%, less than 12%, 11%, less than 11%, 10%, less than 10%, 9%, less than 9%, 8%, less than 8%, 7%, less than 7%, 6%, less than 6%, 5%, less than 5%, 4%, less than 4%, 3.5%, or less than 3.5%, for example, more than 0.4% to 20%, 2% to 15%, 2.5% to 10%, or 3% to 9%, for example, 1% to 4% (especially in the case of heavy fuel oil) or 6% to 9% (especially in the case of very low sulfur fuel oil).

[0051] As a further example, the additives of the present invention reduce carbon dioxide emissions from engines burning marine fuels (including heavy fuel oil and ultra-low sulfur fuel oil) and / or kerosene by more than 0%, or by more than 0%, 0.1%, more than 0.1%, 0.2%, more than 0.2%, 0.3%, more than 0.3%, 0.4%, more than 0.4%, 0.5%, more than 0.5%, 0.6%, more than 0.6%, 0.7%, more than 0.7%, 0.8%, more than 0.8%, 0.9%, more than 0.9%, 1%, or more than 1%, up to 5%. The reduction may be in the range of less than 5%, 4%, less than 4%, 3%, less than 3%, 2%, less than 2%, 1.8%, less than 1.8%, 1.6%, less than 1.6%, 1.4%, or less than 1.4%, for example, more than 0% to 5%, 0.5% to 3%, 0.7% to 1.5%, or 0.9% to 1.4%, for example, 0.4% to 1.5% or 1% to 1.3% (especially in the case of heavy fuel oil) or 0.1% to 1.5% or 0.8% to 1.4% (especially in the case of very low sulfur fuel oil).

[0052] As a further example, the additives of the present invention reduce the fuel smoke number emission (SFOC, International Organization for Standardization (ISO) 3046-1) of engines burning marine fuel (including heavy fuel oil and ultra-low sulfur fuel oil) and / or kerosene by more than 3.6%, or by more than 3.6%, 4%, 4%, 5%, 5%, 6%, 6%, 7%, 7%, 8%, 8%, 9%, 9%, 10%, 10%, 11%, 11%, 12%, 12%, 13%, 13%, 14%, 14%, 15%, 15%, 16%, 16%, 17%, or more than 17% to 50%, less than 50%, 40%, less than 40%, 30%, less than 30%, 25% The reduction may be in the range of %, less than 25%, 22%, less than 22%, 20%, less than 20%, 19%, less than 19%, 18%, or less than 18%, for example, more than 3.6% to 50%, 4% to 20%, 10% to 20%, 11% to 20%, 13% to 20%, 11% to 18%, or 13% to 18%, for example, 4% to 15% or 4% to 12% (especially in the case of heavy fuel oil) or 13% to 20% or 13% to 18% (especially in the case of very low sulfur fuel oil).

[0053] Selected Embodiments Some embodiments of the present invention include: 1. An additive composition for marine fuel or kerosene, wherein the additive composition is: a. A colloidal dispersion of catalyst metal particles, wherein the particles are: i. Nuclei of metallic compounds containing at least one of iron, ruthenium, osmium, cerium, nickel, palladium, and platinum; and ii. Polyalkenyl-substituted carboxylic acids or anhydrides, or derivatives thereof including, Colloidal dispersion; b. Neutral or over-basic alkaline earth metal cleaning agents containing calcium and / or strontium; and c. Carrier fluids miscible with marine fuel oil, heavy fuel oil, marine distilled fuel, and / or residual fuel oil. An additive composition containing the following: 2. The additive composition according to Embodiment 1, wherein the metal compound is an iron compound, a cerium compound, or a mixture thereof, or the metal compound is iron oxide, cerium oxide, or a mixture thereof, and furthermore, iron(III) oxide and / or iron(II,III) oxide. 3. The additive composition according to Embodiment 1, wherein the particle size of the catalyst metal particles is 1 nm to 1 μm, 2 nm to 500 nm, 3 nm to 100 nm, 3 nm to 50 nm, or 5 nm to 15 nm. 4. The additive composition according to Embodiment 1, wherein the overbasic alkaline earth metal cleaning agent forms a second colloidal dispersion in the additive composition having particle sizes of 1 nm to 1 μm, 2 nm to 500 nm, 3 nm to 100 nm, 3 nm to 50 nm, or 5 nm to 15 nm. 5. The additive composition according to Embodiment 1, wherein the polyalkenyl-substituted carboxylic acid or anhydride, or derivatives thereof, is a di-, tri-, or poly-carboxylic acid, or a derivative thereof; or the polyalkenyl-substituted carboxylic acid or anhydride, or derivatives thereof, is a di-, or tri-carboxylic acid, or a derivative thereof; furthermore, the polyalkenyl-substituted carboxylic acid or anhydride, or derivatives thereof, is a dicarboxylic acid, or a derivative thereof. 6. The additive composition according to Embodiment 5, wherein each carboxylic acid group or its derivative is separated from another carboxylic acid group by three or fewer or two or fewer carbon atoms within the polyalkenyl-substituted carboxylic acid. 7. The additive composition according to Embodiment 1, wherein the number-average molecular weight of the polyalkenyl portion is 100-4000, 200-2250, 250-2000, 500-1500, 750-1250, or 850-1100. 8. The additive composition according to Embodiment 1, wherein the polyalkenyl-substituted carboxylic acid or an anhydride, or derivative thereof, is poly(isobutenyl)succinic acid or a derivative thereof. 9. The additive composition according to Embodiment 1, wherein the polyalkenyl-substituted carboxylic acid or anhydride, or derivative thereof, is a fatty acid, optionally the fatty acid is monounsaturated or saturated, and further optionally the fatty acid is selected from capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, caproleic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, brassic acid, nervonic acid, and further optionally the fatty acid is oleic acid. 10. Alkaline earth metal cleaning agents: a. It is overbasic; b. Contains calcium; and / or c. An additive composition according to Embodiment 1, comprising a hydroxybenzoate, salicylate, or sulfonate. 11. The additive composition according to Embodiment 1, wherein the alkaline earth metal cleaning agent contains calcium salicylate, or the alkaline earth metal cleaning agent is an overbasic calcium salicylate cleaning agent, or further, the alkaline earth metal cleaning agent is calcium salicylate made overbasic with calcium hydroxide / calcium carbonate. 12. The additive composition according to Embodiment 1, wherein the degree of carbonation of the alkaline earth metal cleaning agent is 50% to 95%, typically 60% to 90%, more typically 65% ​​to 90%, or 65% to 85%, more typically 70% to 80%. 13. The additive composition according to Embodiment 1, wherein the basicity index of the alkaline earth metal cleaning agent is 0.1-10, 0.5-9, 1-8.5, 1.5-7, 2-5, 2.5-3.5, or about 3. 14. The mass ratio of the colloidal dispersion of catalyst metal particles to the neutral or overbasic alkaline earth metal cleaning agent is 1000:1~1:1000, 100:1~1:100, 10:1~1:10, 5:1~1:5, 3:1~1:3, 2:1~1:2, 1:1~1:2, less than 1:1~1:2, 1:1.1~1:2, 1:1.4~1:1.6, or approximately 1: The additive composition according to Embodiment 1, wherein the molar ratio of the catalyst metal to the alkaline earth metal is in the range of 1.5, or in the range of 1000:1~1:1000, 100:1~1:100, 10:1~1:15, 5:1~1:10, 3:1~1:5, 2:1~1:4, 1:1~1:3, less than 1:1~1:3, 1:1.5~1:2.5, 1:1.8~1:2.2, or approximately 1:2. 15. A marine fuel composition or kerosene composition comprising the additive composition described in Embodiment 1 and marine fuel oil, heavy fuel oil, marine distilled fuel, and / or residual fuel oil. 16. Marine fuel compositions, marine fuel oils, heavy fuel oils, marine distilled fuels, and / or residual fuel oils are: i. Defined in accordance with or meeting the specifications for marine fuels relating to petroleum products of ISO 8217:2017, ISO 8217:2012, ISO 8217:2010, and / or ISO 8217:2005; ii. The sulfur content is 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, or 0.1% by mass or less, as sulfur atoms. iii. Produced from crude oil by fractional distillation, at least partially, or optionally, in the case of marine fuel oil, entirely; iv. Optionally containing one or more additional additives selected from cleaning agents, dispersants, stabilizers, deemulsifiers, anti-emulsifiers, corrosion inhibitors, low-temperature fluidity improvers, pour point depressants and CFPP modifiers, viscosity improvers, lubricity improvers and / or flammability improvers; or v. Composed of any combination of the above i-iv. The marine fuel composition or kerosene composition described in Embodiment 15. 17. a. Metals with a concentration of 1 ppm to 1000 ppm by mass, for example, 5 ppm to 500 ppm, 10 ppm to 100 ppm, 25 ppm to 70 ppm, or 40 ppm to 60 ppm; b. Catalyst metals in mass of 1 ppm to 1000 ppm, for example 2 ppm to 500 ppm, 5 ppm to 200 ppm, 10 ppm to 100 ppm, 12 ppm to 50 ppm, or 15 ppm to 30 ppm, optionally or alternatively, iron; or c. Alkaline earth metals in concentrations of 1 ppm to 1000 ppm by mass, for example, 2 ppm to 500 ppm, 5 ppm to 200 ppm, 10 ppm to 100 ppm, 15 ppm to 60 ppm, or 20 ppm to 40 ppm, optionally or alternatively, calcium A marine fuel composition or kerosene composition according to Embodiment 15, comprising an amount of the additive composition. 18. A method for improving the fuel efficiency, combustion characteristics, and / or emission performance of marine fuel or kerosene, comprising the step of combining marine fuel or kerosene with the additive composition described in Embodiment 1. 19. A method for producing marine fuel or kerosene, comprising the step of combining marine fuel oil, heavy fuel oil, marine distilled fuel, and / or residual fuel oil with the additive composition described in Embodiment 1. 20. Use of the additive composition described in Embodiment 1 to improve the fuel efficiency, combustion characteristics, and / or emission performance of marine fuel or kerosene. 21. Use of an effective small amount of a binary additive combination in the marine fuel or kerosene to improve the fuel efficiency, combustion characteristics, and / or emission performance of the marine fuel or kerosene, wherein the binary additive combination is: (A) a colloidal dispersion of catalyst metal particles, wherein the particles are: (i) a nucleus of a metal compound comprising at least one of iron, ruthenium, osmium, cerium, nickel, palladium, and platinum as defined and identified herein; (ii) a colloidal dispersion comprising a polyalkenyl-substituted carboxylic acid or anhydride or derivative thereof as defined and identified herein; (B) a neutral or overbasic alkaline earth metal cleaning agent comprising calcium and / or strontium as defined and identified herein. Use of a dual-component additive. [Examples]

[0054] The present invention will be illustrated by the following non-limiting embodiments.

[0055] Marine engine information The Caterpillar MaK 6M20, 6-cylinder, 4-stroke test engine, which uses pump-line nozzle injection, was used in the following examples. The specifications of this engine are shown in Table 1 below. [Table 1]

[0056] fuel information To determine the effects of additives on heavy fuel oil (HFO, 1.2% sulfur fuel) and very low sulfur fuel oil (VLSFO, 0.5% sulfur fuel), two different fuels were evaluated using a test engine. The characteristics of the fuels are shown in Table 2 below. [Table 2]

[0057] Operation routine The following operational routines, as shown in Table 3, were used in each experiment. [Table 3] During the experiment, carbon monoxide, carbon dioxide, nitric oxide, and total hydrocarbons in the exhaust gas were measured using an ABB Advanced Optima2000 exhaust gas measurement system, the filter smoke number was measured using an AVL Smokemeter 415S, and fuel consumption was measured using a Krohne OPTIMASS 6400F Coriolis mass flow meter.

[0058] Fuel input During the test period, the additive was injected directly into the fuel line as needed. This was done using a simple high-performance liquid chromatography (HPLC) pump installed to integrate with the engine's fuel system. The fuel system is shown in the schematic diagram in Figure 1 (HFO is used here, but VLSFO can also be used). The additive was introduced in two ways: a method that allows for direct comparative measurement in an active state (with additive) or an inactive state (without additive); and a method that does not involve introducing the additive into the fuel storage tank, although introducing it into the fuel before refueling (e.g., at the refining unit or terminal) is conceivable.

[0059] Example of HFO fuel 1: The operating routine and engine were configured as described above. A 6-cylinder, 4-stroke test engine was used to evaluate the effects of additives on fuel consumption and emissions of a typical high-sulfur heavy fuel oil. The additives were introduced into the fuel system so that they could be added when needed and to prevent contamination of the bulk fuel tank. The following additives were tested: Additive A: Calcium salicylate cleaning agent made overbasic with CaCO3 (carbonation level: approximately 75%) (supplied with a Ca treatment rate of 25 ppm in the fuel) Additive B: Colloidal dispersion of iron(II,III) oxide particles stabilized with poly(isobutene)succinic acid (PIB, number average molecular weight 1000) (supplied with an Fe treatment rate of 20 ppm in the fuel) Ferrocene (supplied with an Fe treatment rate of 25 ppm in the fuel) is combined with a calcium salicylate cleaning agent (supplied with a Ca treatment rate of 30 ppm in the fuel) that has been made overbasic with additive C: CaCO3 (carbonation degree: approximately 75%).

[0060] The additive processing rate could be easily adjusted using the configured dosing system, and the actual processing rate achieved was confirmed by inductively coupled plasma (ICP) measurements of the fuel sample. Data was collected over approximately one hour at each test stage (first with the base fuel, then with the additive fuel, and then back with the base fuel). This allowed for statistical analysis of the data and prevented the misinterpretation of natural biases in measurements conducted throughout the day as the effect of the additives. The results of the effects of the additive on fuel consumption and emissions are shown in detail in Table 4 below. As can be seen from the table, Example 1 of the present invention significantly reduced emissions and fuel consumption (improved fuel efficiency), and in each case, it was superior to the measurement results of Examples 2 to 4. [Table 4]

[0061] Example of VLSFO fuel 2 In the following example, the operating routine and engine were configured as described above. The VLSFO fuel 2 described above was used as the base fuel for the engine. Data was collected over approximately one hour at each test stage (first with the base fuel, then with the additive fuel, and then back with the base fuel). This helps to mitigate the natural bias of measurements taken throughout a day of engine operation, which could be mistakenly attributed to the effects of the additive, resulting in more reliable results. The following additives were tested: Additive A: Calcium salicylate cleaning agent made overbasic with CaCO3 (carbonation level: approximately 75%). Additive B: Colloidal dispersion of iron(II,III) oxide particles stabilized with poly(isobutene)succinic acid (PIB, number average molecular weight 1000) Additive C: Colloidal dispersion of iron(II,III) oxide particles stabilized with oleic acid. Additive D: Ferrocene combined with calcium salicylate cleaning agent made overbasic with CaCO3 (carbonation level: approximately 75%) (supplied with an Fe treatment rate of 20 ppm in the fuel) A magnesium salicylate cleaning agent made overbasic with additive E: MgCO3 (carbonation level: approximately 70%).

[0062] The results of the effects of the additive on fuel consumption and emissions are shown in detail in Table 5 below. As can be seen from the table, Examples 5 and 7 of the present invention significantly reduced emissions and fuel consumption (improved fuel efficiency), and in each case, were superior to the measurement results of Examples 6, 8, and 9. [Table 5]

[0063] Thermogravimetric analysis (TGA) Thermogravimetric analysis (TGA) is a standard technique that can be used to demonstrate the effectiveness of potential combustion enhancers in fuels by measuring the mass loss from a fuel composition as a function of increasing temperature. For example, an increase in mass loss of a fuel composition at low temperatures is an indicator of enhanced effectiveness of fuel additives as combustion enhancers (e.g., improved fuel combustion characteristics) and a reduction in soot buildup and / or emissions by the fuel composition. The thermogravimetric system used was a TA Instruments Q5000 analyzer equipped with a thermobalance and an autosampler with 25 pans. Samples of each composition were placed in the sample pans on the sample cradles surrounding the autosampler platform. The sample test was automated and software-controlled, and the test included tare and loading of the pans, sample weighing, movement of the autosampler, and heating and cooling of the furnace. The recorded sample mass loss was due to high-temperature combustion and volatilization of the sample. The samples were heated from 50°C to 600°C at a heating rate of 10°C per minute. The test was conducted in air.

[0064] The fuel compositions tested included the following: VLSFO fuel 2 (BF1) — Untreated baseline fuel oil for comparison. Composition 1 (IC1) of the present invention is a VLSFO fuel 2 to which a binary additive combination is added. This binary additive combination comprises: (A) a colloidal dispersion of iron(II,III) oxide particles stabilized with poly(isobutene)succinic acid (PIB, number average molecular weight 1000) and added to the fuel at an Fe treatment rate of 20 ppm; and (B) a calcium salicylate cleaning agent overbasicated with CaCO3 (carbonation degree: approximately 75%) and added to the fuel at a calcium treatment rate of 30 ppm. Composition 2 (IC2) of the present invention is a VLSFO fuel 2 to which a binary additive combination is added. This binary additive combination comprises: (A) a colloidal dispersion of cerium oxide particles stabilized with poly(isobutene)succinic acid (PIB, number average molecular weight 1000) and added to the fuel with a cerium treatment rate of 20 ppm; and (B) a calcium salicylate cleaning agent overbasicated with CaCO3 (carbonation degree: approximately 75%) and added to the fuel with a calcium treatment rate of 30 ppm.

[0065] As shown in Figure 2, each fuel composition of the present invention, Composition 1 (IC1), which contains VLSFO fuel 2 and a binary additive mixture in which the metal is iron, and Composition 2 (IC2), which contains VLSFO fuel 2 and a binary additive mixture in which the metal is cerium, exhibit increased mass loss at specific temperatures compared to untreated VLSFO fuel 2 alone (BF1). The increase in mass loss for each fuel composition of the present invention, Composition 1 and Composition 2, is evident over a temperature range of approximately 100°C to 400°C. Therefore, the TGA results demonstrate that each fuel composition of the present invention, Composition 1 and Composition 2, exhibits improved combustion characteristics and / or emission reductions compared to untreated VLSFO fuel 2 alone, over a relatively wide temperature range at a given temperature.

[0066] The dimensions and numerical values ​​disclosed herein should not be understood as strictly limited to the exact numerical values ​​referenced. Instead, unless otherwise specified, each such dimension is intended to mean both the numerical value referenced and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm." All documents cited herein, including cross-referenced or related patents or applications, are incorporated herein by reference in their entirety unless expressly excluded or otherwise limited. No reference to any document constitutes prior art relating to an invention disclosed or claimed herein, nor does it teach, suggest or disclose such invention, either alone or in combination with other reference documents. Furthermore, to the extent that the meaning or definition of a term herein conflicts with the meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term herein shall prevail. While specific embodiments of the present invention have been illustrated and described, it will be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the appended claims are intended to cover all such changes and modifications that fall within the scope and spirit of the invention.

Claims

1. 1. An additive composition for marine fuel or kerosene, said additive composition comprising: a. A colloidal dispersion of catalytic metal particles, said particles comprising: i. a metal compound core containing at least one of iron, ruthenium, osmium, cerium, nickel, palladium, and platinum; and ii. Polyalkenyl-substituted carboxylic acids or anhydrides, or derivatives thereof Contains colloidal dispersions; b. a neutral or overbased alkaline earth metal detergent containing calcium and / or strontium; and c. Carrier fluids miscible with marine fuel oil, heavy fuel oil, marine distillate fuel, and / or residual fuel oil 1. An additive composition comprising:

2. 2. The additive composition of claim 1, wherein the metal compound is a compound of iron, a compound of cerium, or a mixture thereof, or the metal compound is iron oxide, cerium oxide, or a mixture thereof, and further alternatively is iron (III) oxide and / or iron (II, III) oxide.

3. 10. The additive composition of claim 1, wherein the catalytic metal particles have a particle size of 1 nm to 1 μm, 2 nm to 500 nm, 3 nm to 100 nm, 3 nm to 50 nm, or 5 nm to 15 nm.

4. 10. The additive composition of claim 1, wherein the overbased alkaline earth metal detergent forms a second colloidal dispersion in the additive composition having a particle size of 1 nm to 1 μm, 2 nm to 500 nm, 3 nm to 100 nm, 3 nm to 50 nm, or 5 nm to 15 nm.

5. 2. The additive composition of claim 1, wherein the polyalkenyl-substituted carboxylic acid or anhydride, or derivative thereof, is a di-, tri-, or poly-carboxylic acid or derivative thereof; alternatively, the polyalkenyl-substituted carboxylic acid or anhydride, or derivative thereof, is a di- or tri-carboxylic acid or derivative thereof; and further alternatively, the polyalkenyl-substituted carboxylic acid or anhydride, or derivative thereof, is a dicarboxylic acid or derivative thereof.

6. 6. The additive composition of claim 5, wherein each carboxylic acid group or derivative thereof is separated from another carboxylic acid group by no more than 3 or no more than 2 carbon atoms in said polyalkenyl-substituted carboxylic acid.

7. 10. The additive composition of claim 1, wherein the polyalkenyl moiety has a number average molecular weight of 100 to 4000, 200 to 2250, 250 to 2000, 500 to 1500, 750 to 1250, or 850 to 1100.

8. 10. The additive composition of claim 1, wherein said polyalkenyl-substituted carboxylic acid or anhydride, or derivative thereof, is poly(isobutenyl)succinic acid or poly(isobutenyl)succinic anhydride, or derivative thereof.

9. 2. The additive composition of claim 1, wherein the polyalkenyl-substituted carboxylic acid or anhydride, or derivative thereof, is a fatty acid, optionally the fatty acid is monounsaturated or saturated, further optionally the fatty acid is selected from capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, caproleic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, brassidic acid, nervonic acid, and further optionally the fatty acid is oleic acid.

10. The alkaline earth metal detergent comprises: a. is overbased; b. Contains calcium; and / or c) The additive composition of claim 1, comprising a hydroxybenzoate, a salicylate, or a sulfonate.

11. 10. The additive composition of claim 1, wherein the alkaline earth metal detergent comprises calcium salicylate; alternatively, the alkaline earth metal detergent is an overbased calcium salicylate detergent; and further alternatively, the alkaline earth metal detergent is calcium hydroxide / calcium carbonate overbased calcium salicylate.

12. 10. The additive composition of claim 1, wherein the alkaline earth metal detergent has a carbonation level of 50% to 95%, typically 60% to 90%, more typically 65% ​​to 90%, or 65% to 85%, more typically 70% to 80%.

13. 10. The additive composition of claim 1, wherein the alkaline earth metal detergent has a basicity index of 0.1 to 10, 0.5 to 9, 1 to 8.5, 1.5 to 7, 2 to 5, 2.5 to 3.5, or about 3.

14. the weight ratio of the colloidal dispersion of catalytic metal particles of the catalytic metal to the neutral or overbased alkaline earth metal detergent of the alkaline earth metal is in the range of 1000:1 to 1:1000, 100:1 to 1:100, 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1:1 to 1:2, less than 1:1 to 1:2, 1:1.1 to 1:2, 1:1.4 to 1:1.6; 10. The additive composition of claim 1, wherein the molar ratio of said catalytic metal to said alkaline earth metal is at or about 1:1.5, or is in the range of 1000:1 to 1:1000, 100:1 to 1:100, 10:1 to 1:15, 5:1 to 1:10, 3:1 to 1:5, 2:1 to 1:4, 1:1 to 1:3, less than 1:1 to 1:3, 1:1.5 to 1:2.5, 1:1.8 to 1:2.2, or about 1:

2.

15. A marine fuel or kerosene composition comprising the additive composition of any one of claims 1 to 14 and marine fuel oil, heavy fuel oil, marine distillate fuel, and / or residual fuel oil.

16. The marine fuel composition, the marine fuel oil, the heavy fuel oil, the marine distillate fuel, and / or the residual fuel oil comprises: i. is defined in accordance with or meets at least one of the marine fuel specifications for petroleum products in ISO 8217:2017, ISO 8217:2012, ISO 8217:2010, and / or ISO 8217:2005; ii. the sulfur content, as atomic sulfur, is 5% by weight or less, 2% by weight or less, 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less; iii. At least partially, or optionally, in the case of said marine fuel oil, entirely, produced from crude oil by fractional distillation; iv. optionally containing one or more additional additives selected from detergents, dispersants, stabilizers, demulsifiers, anti-emulsifiers, corrosion inhibitors, cold flow improvers, pour point depressants and CFPP modifiers, viscosity improvers, lubricity improvers, and / or flammability improvers; or v. Any combination of the above i to iv 16. A marine fuel or kerosene composition according to claim 15.

17. a. 1 ppm to 1000 ppm by mass of metal, e.g., 5 ppm to 500 ppm, 10 ppm to 100 ppm, 25 ppm to 70 ppm, or 40 ppm to 60 ppm; b. 1 ppm to 1000 ppm by mass, e.g., 2 ppm to 500 ppm, 5 ppm to 200 ppm, 10 ppm to 100 ppm, 12 ppm to 50 ppm, or 15 ppm to 30 ppm of a catalytic metal, preferably iron; or c. 1 ppm to 1000 ppm by mass, e.g., 2 ppm to 500 ppm, 5 ppm to 200 ppm, 10 ppm to 100 ppm, 15 ppm to 60 ppm, or 20 ppm to 40 ppm of an alkaline earth metal, preferably calcium 16. The marine fuel or kerosene composition of claim 15, comprising the additive composition in an amount of

18. 15. A method of improving the fuel economy, combustion characteristics and / or emissions performance of a marine fuel or kerosene, the method comprising combining said marine fuel or said kerosene with an additive composition according to any one of claims 1 to 14.

19. 15. A method of producing a marine fuel or kerosene composition, the method comprising combining a marine fuel oil, a heavy fuel oil, a marine distillate fuel, and / or a residual fuel oil with the additive composition of any one of claims 1 to 14.

20. 15. Use of an additive composition or binary combination of additives according to any one of claims 1 to 14 to improve the fuel economy, combustion characteristics, and / or emissions performance of a marine fuel or kerosene, said binary combination comprising: (A) a colloidal dispersion of catalytic metal particles as defined in any one of claims 1 to 14, said particles comprising: (i) a core of a metal compound comprising at least one of iron, ruthenium, osmium, cerium, nickel, palladium, and platinum; (ii) a colloidal dispersion comprising a polyalkenyl-substituted carboxylic acid or anhydride or derivative thereof as defined in any one of claims 1 to 14; and (B) a calcium and / or strontium-containing neutral or overbased alkaline earth metal detergent as defined in any one of claims 1 to 14.

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