Marine fuel composition comprising additivated cnsl

Abstract

The invention relates to a marine fuel composition comprising additivated CNSL and an improved cetane number. The composition comprises: - 65% to 99% by mass of a first component (a) comprising a fossil base, this first component having a sulfur content of at most 1.5% by mass, preferably of at most 1% by mass, more preferably of at most 0.7% by mass, and a flash point of at least 60°C, - 1% to 35% by mass of a second component (b) consisting of cashew nut shell liquid (CNSL), - 500 to 5000 ppm by mass of an additives composition (c) with respect to the sum of the masses of components (a) and (b), said additives composition (c) comprising: (i) one or more cetane improver additives, (ii) one or more deposit reducing additives.

Description

[0001] DESCRIPTION

[0002] TITLE: MARINE FUEL COMPOSITION COMPRISING CNSL ADDITIVE

[0003] technical field

[0004]

[0001] The present invention relates to a marine fuel composition comprising added CNSL. CNSL, short for "Cashew nut shell liquid," is the liquid extracted from the shell of the cashew nut (Anacardium occidentale). The resulting composition has an improved cetane number.

[0005] Previous art

[0006]

[0002] Marine fuels are usually manufactured by mixing a residue of fossil origin (atmospheric residue, vacuum residue or viscoreduction residue) or a distillate of fossil origin with one or more fluxing agents usually of petroleum origin.

[0007]

[0003] In order to reduce the environmental impact of marine fuels, producers are seeking to incorporate more and more renewable components into their manufacturing process. In particular, producers are seeking to manufacture fuels that preferably have a low impact on greenhouse gases such as carbon dioxide, and a low sulfur content, as the objective is to reduce sulfur emissions, particularly in Arctic regions.

[0008]

[0004] The applicant described in document W02023 / 094301A1 a marine fuel base comprising a renewable component of the methyl ester type derived from fatty acids of vegetable or animal origin (also referred to by the acronym EMAG or FAME in English). The addition of this renewable component improves the viscosity, pour point, and stability of a petroleum residue.

[0009]

[0005] The search for other components of renewable origin that can be incorporated into marine fuels is also constant.

[0010]

[0006] Document WO 2023 / 037049 describes a marine fuel mixture comprising from 0.5 to 50% by volume of refined CNSL comprising at least 50% by mass of cardanol.

[0011]

[0007] There is nevertheless a constant need to improve compositions usable as marine fuel comprising a renewable component.

[0012] Description of the invention

[0013]

[0008] The present invention thus aims to provide a marine fuel composition containing added CNSL exhibiting improved cetane number properties. Another objective of the present invention is to provide a low-sulfur marine fuel composition. Yet another objective is to provide a marine fuel composition with a renewable component that can be used with current marine fuel logistics.

[0014]

[0009] The applicant discovered that the use of a particular additive composition, based on the combination of a cetane-enhancing additive and a deposition-reducing additive, exhibits significant and unexpected effectiveness in increasing the cetane of a composition comprising a fossil base and CNSL.

[0015]

[0010] The invention relates to a marine fuel composition comprising, in particular, the following:

[0016]

[0011] - 65 to 99% by mass of a first component (a) comprising a fossil base, this first component having a sulfur content of at most 1.5% by mass, preferably at most 1% by mass, more preferably at most 0.7% by mass, and a flash point of at least 60 °C,

[0017] 1 to 35% by mass of a second component (b) consisting of cashew nut shell liquid (CNSL), from 500 to 5000 ppm by mass of a composition (c) of additives relative to the sum of the masses of components (a) and (b), said composition (c) of additives comprising:

[0018] (i) one or more additives improving the cetane number,

[0019] (ii) one or more deposit-reducing additives.

[0020]

[0012] Surprisingly, the addition of an additive composition comprising both one or more cetane number-enhancing additives and one or more sediment-reducing additives results in a greater improvement in the cetane number, in particular the estimated cetane number (also denoted ECN), of the composition compared to the addition of only additive(s) (i) or additive(s) (ii), whereas the addition of additive(s) (i) alone has no effect and the addition of additive(s) (ii) alone degrades the cetane number of the composition.

[0013] This synergy is observed for a component (a), including in particular a fossil residue or fossil distillate, and a component (b) that is CNSL, in particular distilled and / or refined technical CNSL.

[0021]

[0014] This synergy on the improvement of the ECN of the composition is further increased when the composition of additives also includes at least one lubricant additive (iv) and / or at least one antioxidant additive (v).

[0022]

[0015] Preferably, the proportions of components (a) and (b) are such that the composition according to the invention has a sulfur content of at most 0.5% by mass and a flash point of at least 60 °C.

[0023]

[0016] The invention also relates to a method for manufacturing a marine fuel composition in which said composition results from mixing: 65 to 99% by mass of a first component (a) comprising a fossil base, this first component having a sulfur content of at most 1.5% by mass, preferably at most 1% by mass, more preferably at most 0.7% by mass and a flash point of at least 60 °C, 1 to 35% by mass of a second component (b) consisting of cashew nut shell liquid (CNSL), and 500 to 5000 ppm by mass of a composition (c) of additives relative to the sum of the masses of components (a) and (b), said composition (c) of additives comprising:

[0024] (i) one or more additives improving the cetane number,

[0025] (ii) one or more deposit-reducing additives.

[0017] Advantageously, the mixture of components (a) and (b) is carried out in proportions such that the resulting composition has a sulfur content of at most 0.5% by mass and a flash point of at least 60 °C.

[0026]

[0018] The invention further relates to the use of an additive composition to improve the cetane number of a mixture containing 65 to 99% by mass of a first component (a) comprising a fossil base and having a sulfur content of at most 1.5% by mass, preferably at most 1% by mass, more preferably at most 0.7% by mass, and a flash point of at least 60°C, and 1 to 35% by mass of a second component (b) consisting of cashew nut shell liquid (CNSL), said additive composition comprising:

[0027] (i) one or more additives improving the cetane number,

[0028] (ii) one or more deposit-reducing additives, and being added to the mixture in an amount of 500 to 5000 ppm by mass.

[0029]

[0019] Advantageously, the mixture of components (a) and (b) has a sulfur content of at most 0.5% by mass and a flash point of at least 60 °C.

[0030] Detailed description of the invention

[0031]

[0020] The terms "including" and "includes" as used herein are synonymous with "including", "includes" or "contains", "containing", and are inclusive or boundless and do not exclude additional features, elements or unspecified method steps.

[0032]

[0021] The expressions % by weight and % by mass (also noted % m) have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0033]

[0022] Similarly, and unless explicitly stated otherwise, the standards mentioned in the rest of the description correspond to the standard in force on December 17, 2024.

[0023] Unless otherwise stated, the measurements given in parts per million (ppm) are expressed in mass.

[0034]

[0024] An atmospheric distillate is obtained from the atmospheric distillation of crude oil.

[0035]

[0025] A vacuum distillate is obtained from the vacuum distillation of an atmospheric residue or another residue of petroleum origin.

[0036]

[0026] An atmospheric residue is obtained from the atmospheric distillation of crude oil (bottom of the atmospheric distillation column).

[0037]

[0027] A vacuum residue is obtained from the vacuum distillation of an atmospheric residue (bottom of the vacuum distillation column).

[0038]

[0028] A residue from a viscoreduction process, also called viscoreduction residue or viscoreduced residue, results from the transformation of a residue under vacuum by viscoreduction or "visbreaking".

[0039]

[0029] Boiling points as mentioned herein are measured at atmospheric pressure, unless otherwise specified. An initial boiling point is defined as the temperature at which the first vapor bubble forms. A final boiling point is the highest temperature attainable during distillation. At this temperature, no more vapor can be transported to a condenser. The determination of the initial and final boiling points relies on techniques known in the trade, and several methods adapted according to the distillation temperature range are applicable, for example, NF EN 15199-1 or ASTM D2887 for measuring the boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, and ASTM D7500, D86, or D1160 for distillates.

[0040]

[0030] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0041]

[0031] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0042]

[0032] The concentration of heteroatoms in the hydrocarbon matrix can be determined by any method known in the art. In particular, relevant characterization methods include X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), and inductively coupled plasma atomic emission spectrometry (ICP-AES). Analytical scientists are able to identify the most suitable method for measuring each metal and, more generally, each heteroatom, depending on the hydrocarbon matrix considered. The oxygen content can be measured according to ASTM D5622- / D2504-88. The nitrogen content can be measured according to ASTM D5291.

[0043]

[0033] The halogen content, in particular chlorine, can be measured according to the standard: EN 14077.

[0044]

[0034] The density at 15°C is measured according to ISO 12185.

[0045]

[0035] Viscosity here is kinematic viscosity, measured at 50°C or 100°C, for example according to ISO 3104.

[0046]

[0036] The pour point is measured according to ISO 3016.

[0047]

[0037] The sulfur content can be measured according to ISO 8754 or ASTM D4294.

[0048]

[0038] The calculated carbon aromaticity index (CCAI) is calculated according to the Lewis equation (recalled in standard NF ISO 8217).

[0049]

[0039] The asphaltene content can be measured according to standard NF T60-115.

[0050]

[0040] The flash point can be measured according to standard NF EN ISO2719.

[0051]

[0041] The estimated cetane number (ECN) is measured according to standard IP 541.

[0052]

[0042] In the following description, the different embodiments described, and in particular the preferred embodiments of each step, can be combined according to the objective sought.

[0053]

[0043] First component (a)

[0054]

[0044] The first component comprises, or is made up of, a fossil base. This first component is advantageously a first fossil component.

[0055]

[0045] The term "fossil base" or "fossil-derived base" or "fossil component" refers to a base / component consisting solely of hydrocarbons derived from crude oil, or even from shale oil or oil sands. Most often, the fossil base according to the invention is derived from crude oil.

[0056]

[0046] According to the invention, the first component has a sulfur content of at most 1.5% by mass, for example from 0.001 to 1.5% by mass, preferably at most 1% by mass, more preferably at most 0.7% by mass, or even at most 0.5% by mass, and a flash point of at least 60°C, for example from 60 to 150°C.

[0057]

[0047] It may be possible to use a first component complying with the specifications for marine residual fuels of ISO 8217:2024, in particular complying with the specifications required for one of the categories of marine distillate listed in Table 1 of ISO 8217:2024 or for one of the categories of marine residual fuel listed in Tables 2 and 4 of ISO 8217:2024.

[0058]

[0048] The first component (a) comprises a fossil base which can be selected from an atmospheric distillate, a vacuum distillate, an atmospheric residue, a vacuum residue and a viscoreduction residue.

[0059]

[0049] The boiling range of distillates is typically from 140 to 370 °C.

[0060]

[0050] By "distillate" is meant a hydrocarbon fraction having a boiling point at T10 of 140°C or more and a distillation point at T90 of 370°C or less.

[0061]

[0051] An atmospheric residue is defined as a background fraction having a boiling point at T10 of 149 °C or more, or 350 °C or more.

[0062]

[0052] A vacuum residue is defined as a bottom fraction having a boiling point at T10 of 500 °C or more, or 538 °C or more, or 565 °C or more.

[0063]

[0053] Advantageously, the fossil base of the first component may exhibit one or more of the following characteristics:

[0064]

[0054] - a sulfur content of at most 1.5% by mass, preferably at most 1% by mass, or even at most 0.7% by mass, and typically at least 0.1 or 0.5% by mass,

[0065]

[0055] - a density at 15 °C of 845 to 1060 kg / m³ 3 .

[0066]

[0056] By way of example, a fossil base of the residue type includes:

[0067]

[0057] - heavy fuel oils or HFOs (in English “Heavy fuel oil”,

[0068]

[0058] - low density heavy fuel oils (“HFO low density”),

[0069]

[0059] - low sulfur heavy fuel oils or VLSFO (in English "Very Low Sulphur Fuel Oils")

[0070] Sulfur Fuel Oil”),

[0071]

[0060] - low sulfur and low viscosity heavy fuel oils or "VLSFO low viscosity".

[0072]

[0061] A fossil base of distillate type includes marine diesels or MDO (in English “Marine Diesel oil”.

[0073]

[0062] In one embodiment, at least one hydrocarbon residue of the first component may have a density at 15 °C of 950 to 1060 kg / m³ 3 and / or a viscosity at 100 °C of 20 to 2500 mm 2 / s.

[0074]

[0063] When the residue is a vacuum residue, it may exhibit at least one of the following characteristics:

[0075]

[0064] for a sulfur content of at most 1.5% by mass, preferably at most 1% by mass, more preferably at most 0.5% by mass, an asphaltene content of less than 3% by mass, a carbon residue of less than 15% by mass,

[0076]

[0065] regardless of the sulfur content, a Sa value measured according to ASTM D7157 greater than 0.75,

[0077]

[0066] regardless of the sulfur content, a density at 15 °C of 950 to 1000 kg / m³ 3 ,

[0078]

[0067] regardless of the sulfur content, a viscosity at 100 °C of 20 to 2500 mm 2 / s,

[0079]

[0068] regardless of the sulfur content, a viscosity at 50 °C of 150 to 600,000 mm 2 / s.

[0080]

[0069] When the residue is a visbreaking residue, it may have at least one of the following characteristics:

[0070] for a sulfur content of at most 1.5% by mass, preferably at most 1% by mass, more preferably at most 0.5% by mass: an asphaltene content greater than 10% by mass, a carbon residue greater than 20% by mass,

[0081]

[0071] regardless of the sulfur content, a Sa value measured according to ASTM D7157 less than 0.75,

[0082]

[0072] regardless of the sulfur content, a density at 15 °C of 950 to 1060 kg / m³ 3 ,

[0073] regardless of the sulfur content, a viscosity at 100 °C of 80 to 1500 mm 2 / s,

[0083]

[0074] regardless of the sulfur content, a viscosity at 50 °C of 1700 to 300000 mm 2 / s.

[0084]

[0075] When the residue is an atmospheric residue, it may have at least one of the following characteristics: a density at 15°C of 845 to 990 kg / m³ 3 , a viscosity at 100 °C of 10 to 180 mm 2 / s, a viscosity at 50 °C of 50 to 6200 mm 2 / s.

[0085]

[0076] In addition to at least one hydrocarbon residue, the first component may further comprise at least one fluxing agent of petroleum origin and / or renewable origin.

[0086]

[0077] This fluxing agent can be added in quantities enabling the desired sulfur content of the first component to be obtained.

[0087]

[0078] The petroleum-based fluxing agent is, for example, chosen from:

[0088]

[0079] - diesel fuels derived from the direct distillation of petroleum: kerosene, lamp oil, light diesel, medium diesel, heavy diesel,

[0089]

[0080] - the products of vacuum distillation of atmospheric residue: light vacuum diesel, medium vacuum diesel, heavy vacuum diesel, distillate,

[0090]

[0081] - the products of atmospheric or vacuum distillation of the effluents from the conversion units: viscoreducing diesel, viscoreducing distillate,

[0091]

[0082] - products from catalytic cracking units and desulfurization and hydrodesulfurization units: catalytic cracker gas oil (LCO), heavy catalytic cracker gas oils (HCO, clear oil, slurry), desulfurized gas oil, gas oil and bleed (residue) from hydrodesulfurization units,

[0092]

[0083] - products from steam cracking units: pyrolysis oil or gasoline.

[0093]

[0084] The fluxant of renewable origin is for example chosen from among the alkyl ester(s) of fatty acids.

[0094]

[0085] It can be selected from methyl esters, ethyl esters, propyl esters, alone or in mixture, preferably methyl esters, ethyl esters, alone or in mixture, for example methyl esters (EMAG). In a preferred embodiment, the fluxing agent of renewable origin consists solely of alkyl esters, in particular methyl esters, ethyl esters and / or propyl esters, preferably methyl esters and / or ethyl esters, without any other component, in particular of the alcohol type.

[0095]

[0086] The fluxing agent may consist solely of petroleum-based fluxing agent, solely of renewable-based fluxing agent, or be a mixture of petroleum-based and renewable-based fluxing agents. The content of petroleum-based and / or renewable-based fluxing agent in the first component may be chosen according to the desired sulfur content and / or viscosity for component (a).

[0087] Typically, the fluxing agent content of the first component (a) may be from 0 to 45% by mass, the remainder being the fossil base.

[0096]

[0088] In particular, the renewable flux content of the first component (a) can be from 0 to 30% by mass, the remainder being made up of the fossil base, or of the fossil base and a petroleum flux, preferably of the fossil base.

[0097]

[0089] The renewable flux content of the first component, and in particular the methyl ester content, can be determined by the IP579 or ASTM D7963 test methods, as described in ISO 8217-2024.

[0098]

[0090] In one embodiment, the first component (a) consists of a fossil base, and optionally of at least one fluxant chosen from a petroleum-based fluxant and a renewable-based fluxant, in particular as previously described.

[0099]

[0091] Second component (b) consisting of cashew nut shell liquid (CNSL)

[0100]

[0092] Cashew nut shell liquid, or CNSL, is a natural oil derived from cashew nut shells. The main components of CNSL are phenolic compounds: anacardic acid, cardol, and cardanol. Methyl cardol may also be present, but in trace amounts (< 5% by mass).

[0101]

[0093] Natural CNSL is typically obtained by extraction using a low-boiling-point solvent or mechanically without heating. It contains, for example, 40 to 85% by mass of anacardic acid, 15 to 45% by mass of cardol, and 10 to 25% by mass of cardanol. It generally also contains methylcardol (approximately 1 to 4% by mass). Other compounds may be present in trace amounts.

[0102]

[0094] The technical CNSL is obtained by hot processes, in particular by high-temperature roasting, e.g. >200°C.

[0103]

[0095] Technical CNSL contains a reduced amount of anacardic acid compared to natural CNSL, due to partial decarboxylation during heating or roasting. In some cases, the decarboxylation is even complete, and the CNSL no longer contains any anacardic acid.

[0104]

[0096] The technical CNSL may comprise from 0 to 6% by mass of organic acids, including anacardic acid, from 55 to 95% by mass of cardanol, and from 4 to 40% of cardol. It generally also contains methylcardol (approximately 2 to 6% by mass) and other polymeric compounds. The polymeric compounds may optionally be removed by distillation.

[0105]

[0097] By "crude undecarboxylated CNSL" or "natural CNSL" is meant a CNSL that has not undergone, or has only partially undergone, decarboxylation of anacardic acid. Crude undecarboxylated CNSL is therefore characterized by the presence of anacardic acid as the major species in the mixture.

[0106]

[0098] The CNSL used in the present invention is preferably technical CNSL, optionally distilled and / or refined, for example by hydrotreatment.

[0107]

[0099] The CNSL used in the present invention may have an acid value of 0.1 to 20 mg KOH / g, preferably of 0.1 to 10 mg KOH / g, in particular measured according to ASTM D664.

[0108]

[0100] A technical CNSL typically has an acid value of 0.1 to 10 mg KOH / g, preferably 0.1 to 9 mg KOH / g, in particular measured according to ASTM D664.

[0101] A distilled and / or refined technical CNSL typically has an acid value of 0.1 to 5 mg KOH / g, preferably 0.1 to 2 mg KOH / g, in particular measured according to ASTM D664.

[0109]

[0102] Composition (c) of additives

[0110]

[0103] The composition (c) of additives used in the present invention comprises:

[0111]

[0104] (i) one or more additives improving the cetane number,

[0112] (ii) one or more deposit-reducing additives.

[0113]

[0105] In a preferred embodiment, the composition (c) of additives used in the present invention comprises:

[0114]

[0106] (i) one or more cetane number improving additives selected from alkyl nitrates, aryl peroxides and alkyl peroxides, and preferably from alkyl nitrates of formula R-NO3, with R an alkyl radical comprising 2 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and even better the additive (i) is 2-ethylhexyl nitrate,

[0115]

[0107] (ii) one or more deposit-reducing additives selected from (ii)(1) quaternary ammonium salts other than betaines, (ii)(2) amido alkyl betaines, (ii)(3) non-quaternary polyisobutylene succinimides, and mixtures thereof, in particular from quaternary ammonium salts other than betaines and amido alkyl betaines, and preferably from (ii)(1) quaternary ammonium salts other than betaines and (ii)(2) amido alkyl betaines, and optionally the mass ratio of the amount of the first additive (ii)(1) to the amount of the second additive (ii)(2) is in the range of 1:5 to 5:1, preferably 1:4 to 4:1.

[0116]

[0108] The mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (ii) may advantageously be in the range of 4:1 to 1:4, preferably from 1:3 to 3:1.

[0117]

[0109] In certain embodiments, the composition of additives (c) according to the invention, and in particular its preferred embodiments, may further comprise:

[0118]

[0110] (iii) one or more antioxidant additives, preferably chosen from compounds having at least one alkylphenol group in their structure, and in particular compounds chosen from the preferred compounds described below, and / or

[0119]

[0111] (iv) one or more lubrication additives or anti-wear agents, preferably chosen from the group consisting of fatty acids and their ester or amide derivatives, and in particular compounds chosen from the preferred compounds described below.

[0120]

[0112] Advantageously, the mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (iii) can be in the range of 60:1 to 1:1, preferably from 30:1 to 1:1.

[0121]

[0113] Advantageously, the mass ratio of the quantity of additive(s) (ii) to the quantity of additive(s) (iv) can be in the range of 30:1 to 1:1, preferably from 10:1 to 1:1.

[0122]

[0114] Additive (i) improving the cetane number

[0123]

[0115] The invention implements as additives (i) one or more cetane number improving additives, also known as procetane additives or cetane booster additives.

[0124]

[0116] The additive(s) (i) may be selected, in particular, from alkyl nitrates and aryl or alkyl peroxides.

[0117] Among the aryl peroxides, benzyl peroxide is a notable example. Among the alkyl peroxides, tert-butyl peroxide is a notable example.

[0125]

[0118] The additive(s) (i) are preferably chosen from alkyl-nitrates, and more preferably those of formula R-NO3 with R an alkyl radical, in particular with a linear or branched chain, comprising from 2 to 12 carbon atoms, preferably from 4 to 8 carbon atoms.

[0126]

[0119] A particularly preferred additive (i) is 2-ethyl hexyl nitrate, also noted as 2-EHN.

[0127]

[0120] Preferably, the total content of cetane number improving additive(s) (i) in the composition ranges from 5 to 5,000 ppm by weight, preferably from 5 to 1,000 ppm by mass, more preferably from 10 to 500 ppm by mass, relative to the sum of the masses of components (a) and (b).

[0128]

[0121] Additive (ii) deposit reducer

[0129]

[0122] The additive composition used further comprises one or more detergent additive(s) (ii), also referred to as deposit-reducing additive(s), in particular selected from (ii)(1) quaternary ammonium salts other than betaines, (ii)(2) amido alkyl betaines, (ii)(3) non-quaternary polyisobutylene succinimides (namely polyisobutylene succinimides not containing a quaternary ammonium group) and mixtures thereof, in particular one or more detergent additive(s) (ii) selected from (ii)(1) quaternary ammonium salts other than betaines and (ii)(2) amido alkyl betaines, in particular alone or in mixture.

[0130]

[0123] In a preferred embodiment, additives (ii) shall be used at least one first additive (ii)(1) selected from the different quaternary ammonium salts of betaines, as previously described, and at least one second additive (ii)(2) selected from the amido alkyl betaines, as previously described, the mass ratio of the quantity of the first additive (ii)(1) to the quantity of the second additive (ii)(2) being in the range of 1:5 to 5:1, preferably 1:4 to 4:1.

[0131]

[0124] In a preferred embodiment, the mass ratio of the quantity of the first additive (ii)(1) to the quantity of the second additive (ii)(2) being in the range of 1:1 to 2.5:1, more preferably of 1.5:1 to 2.1:1.

[0132]

[0125] For example, the additives described in patent EP4157971 B1 filed by the applicant and defined below may be used.

[0133]

[0126] Preferably, the total content of deposit-reducing additive(s) (ii) in the composition ranges from 5 to 5000 ppm by mass, preferably from 5 to 1000 ppm by mass, more preferably from 10 to 500 ppm by mass, relative to the sum of the masses of components (a) and (b).

[0134]

[0127] (H)(1) Quaternary ammonium salts

[0135]

[0128] In a first embodiment, the quaternary ammonium salt is obtained by reaction with a quaternizing agent of a nitrogen compound comprising a tertiary amine function, this nitrogen compound being the product of the reaction of an acylation agent substituted by a hydrocarbon group and a compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols.

[0136]

[0129] In a second embodiment, the quaternary ammonium salt is selected from quaternized PIBA (polyisobutylene amine) compounds, or from quaternized polyether amines.

[0130] According to the first embodiment, which is preferred, said nitrogen compound is the product of the reaction of an acylation agent substituted with a hydrocarbon group and a compound comprising both an oxygen atom or a nitrogen atom capable of condensing with said acylation agent (i.e. at least one group selected from primary amines, secondary amines and alcohols) and a tertiary amine group.

[0137]

[0131] The acylation agent is advantageously chosen from mono- or polycarboxylic acids and their derivatives, in particular their ester, amide, or anhydride derivatives. The acylation agent is preferably chosen from succinic, phthalic, and propionic acids and the corresponding anhydrides, for example, polyisobutenylsuccinic anhydride.

[0138]

[0132] In this embodiment, the acylation agent is substituted by a hydrocarbon group. A "hydrocarbon" group is defined as any group having a carbon atom directly attached to the rest of the molecule (i.e., to the acylation agent) and having predominantly aliphatic hydrocarbon character. Preferably, the hydrocarbon substituents are purely aliphatic hydrocarbons and comprise from 8 to 200 carbon atoms. The hydrocarbon substituent of the acylation agent preferably has a number-average molecular weight (Mn) of between 160 and 2800.

[0139]

[0133] According to a preferred embodiment, the hydrocarbon substituent of the acylation agent is a polyisobutene group, also called polyisobutylene (PIB). Highly reactive polyisobutenes (PIB) are particularly preferred. Highly reactive polyisobutenes (PIB) are defined as polyisobutenes (PIB) in which at least 50 mole percent, preferably at least 70 mole percent or more, of the terminal olefinic double bonds are of the vinylidene type as described in document EP0565285. In particular, preferred PIBs are those having more than 80 mole percent and up to 100 mole percent of terminal vinylidene groups as described in document EP1344785.

[0140]

[0134] According to a particularly preferred embodiment, the acylation agent substituted by a hydrocarbon group is a polyisobutenyl-succinic anhydride (PI BSA).

[0141]

[0135] Said compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols is typically selected from the following amines of formula (I) or (II):

[0142]

[0136]

[0143]

[0137]

[0144]

[0138] in which:

[0145]

[0139] R6 and R7 are identical or different and represent, independently of each other, an alkyl group having from 1 to 22 carbon atoms, preferably having from 1 to 5 carbon atoms;

[0146]

[0140] X is an alkylene group having from 1 to 20 carbon atoms, preferably from 1 to 5 carbon atoms;

[0147]

[0141] m is an integer between 1 and 5;

[0148]

[0142] n is an integer between 0 and 20; and

[0149]

[0143] R8 is a hydrogen atom or an alkyl group from C1 to C22.

[0150]

[0144] According to a particularly preferred embodiment, the nitrogen compound is the reaction product of a succinic acid derivative substituted by a hydrocarbon group, preferably a polyisobutenyl-succinic anhydride, and an alcohol or an amine also comprising a tertiary amine group, in particular a compound of formula (I) or (II) as described above, and more preferably a compound of formula (I).

[0151]

[0145] According to a particular embodiment, the quaternizing agent is chosen from the constituent group of dialkyl sulfates, carboxylic acid esters; alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides optionally in mixture with an acid, alone or in mixture, preferably from hydrocarbon epoxides and carboxylic acid esters, more preferably from styrene oxide and propylene oxide, and better still, the quaternizing agent is propylene oxide.

[0152]

[0146] The additive (ii)(1) may advantageously be chosen from polyisobutylene succinimides functionalized with a quaternary ammonium group.

[0153]

[0147] (H)(2) Amido alkyl betaines

[0154]

[0148] Amido alkyl betaines are advantageously chosen from among the amido alkyl betaines, of the following formula (III):

[0155]

[0149]

[0156]

[0150] in which:

[0157]

[0151] R1 is a C1 to C34 hydrocarbon chain, linear or branched,

[0158]

[0152] R2 is a hydrogen atom or a C1 to C15 hydrocarbon chain

[0153] R3 is a C1 to C15 hydrocarbon chain, and

[0159]

[0154] R4 and R5 are identical or different and chosen independently of each other from a hydrogen atom and a hydrocarbon chain in C1 to C10, preferably in C1 to C6, it being understood that the groups R4 and R5 may contain one or more nitrogen groups and / or may be linked together to form one or more rings.

[0160]

[0155] In a preferred embodiment, the alkyl betaine amido of formula (III) may comprise one or more of the following features:

[0161] R1 is a C8 to C30 hydrocarbon chain, linear or branched, preferably C12 to C24, more preferably C16 to C20; R2 is a hydrogen atom or a C1 to C8 hydrocarbon chain, preferably a hydrogen atom.

[0162] R3 is a hydrocarbon chain in C1 to C8, preferably in C2 to C4, R4 and R5 are identical or different and chosen independently of each other from a hydrogen atom and a hydrocarbon chain in C1 to C6, it being understood that the groups R4 and R5 may contain one or more nitrogen groups and / or may be linked together to form a ring; preferably R4 and R5 are identical and represent a methyl group or an ethyl group and more preferably a methyl group.

[0163]

[0156] The additive of formula (III) can be obtained by reaction:

[0164]

[0157] (a) of a tertiary amine substituted with a hydrocarbon group selected from the (C8-C30 alkyl) amidopropyldi(C1-C4 alkyl)amines and the (C8-C30 alkenyl) amidopropyldi(C1-C4 alkyl)amines; preferably from the (C8-C30 alkyl) amidopropyldimethylamines and the (C8-C30 alkenyl) amidopropyldimethylamines; preferably oleylamidopropyl dimethylamine with

[0165]

[0158] (b) acetic acid substituted by a halogen, or one of its salts, or one of its ester or amide derivatives; preferably sodium chloroacetate;

[0166]

[0159] said reaction product being preferably devoid of non-covalent anionic species.

[0167]

[0160] Preferably, compound (a) is oleylamidopropyl dimethylamine and compound (b) is sodium chloroacetate.

[0168]

[0161] (H)(3) Dolvsiobutylene succinimide non-quaternary

[0169]

[0162] According to a preferred embodiment, said deposit-reducing additive (ii)(3) results from the condensation of: a compound A consisting of a dicarboxylic acid substituted by a polyisobutylene group or an anhydride of such a diacid, with a compound B consisting of a primary polyamine of the general formula (IV) below:

[0170]

[0163] H2N-[-(CHR9 -(CH2) P -CHR10) n -NH] m -H (IV) in which R9 and R10, identical or different, represent hydrogen or a hydrocarbon group comprising from 1 to 4 carbon atoms, n is an integer ranging from 1 to 3, m is an integer ranging from 1 to 10, preferably from 1 to 4; and p is an integer equal to 0 or 1.

[0171]

[0164] In a preferred embodiment, said deposit reducing additive (ii)(3) is obtained by condensation of compound A with compound B, used in quantities such that the molar ratio A / B is in the range of 1:1 to 1:3. Preferably, the molar ratio A / B is in the range of 1:1.1 to 1:2, even more preferably the molar ratio A / B is in the range of 1:1.1 to 1:1.5.

[0172]

[0165] Said deposit reducing additive (ii)(3) can in particular be obtained by condensation of 60 to 90% by weight of compound A, and of 10 to 30% by weight of compound B.

[0173]

[0166] The average molar mass of compounds A according to the present invention varies from 200 to 3000, preferably from 200 to 2000 g / mol, preferably from 200 to 1500 g / mol, and even more preferably from 900 to 1300 g / mol. These compounds are well known from the prior art.

[0174]

[0167] Among the primary polyamines according to formula (IV), the polyamines of the group consisting of diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine and their substituted derivatives, or mixtures thereof, are preferred.

[0175]

[0168] The mixing of these compounds A and B can be done indifferently in the order detailed below, or in a different order.

[0176]

[0169] In a preferred mode, compound B, i.e. the primary polyamine of formula (IV) is added to compound A, i.e. the acidic carboxylic hydrocarbon(s) or anhydride(s).

[0177]

[0170] Polyamine B is added gradually in an organic solvent, then to the solution of the carboxylic hydrocarbon mixture at room temperature, the mixture is then heated between 65 and 250°C, and preferably between 80 and 220°C, for 5 to 30 hours.

[0178]

[0171] The organic solvent required for solubilizing the primary polyamine is chosen with a boiling point between 65 and 250°C, and preferably between 80 and 220°C, and its ability to remove the water formed by condensation of the polyamine onto compound A by azeotropic distillation of the water / solvent mixture. The solvent is chosen from the group consisting of benzene, toluene, xylenes, ethylbenzene, and commercial hydrocarbon fractions, for example, those distilling from 190 to 209°C and containing 99% by weight of aromatic compounds.

[0179]

[0172] According to another embodiment of the invention, a mixture of solvents may be used, in particular a mixture of xylenes, or even a xylene / alcohol mixture, preferably the alcohol being ethyl-2-hexanol, in order to facilitate the homogeneity of the medium and to promote the kinetics of the reaction.

[0180]

[0173] After the end of the addition of the primary polyamine B, heating is maintained under reflux until complete removal of water, for 0.5 to 7 hours, preferably 1 to 5 hours.

[0181]

[0174] Additives (iii) antioxidant

[0182]

[0175] The antioxidant additive (iii) is preferably chosen from alkyl phenol compounds and more specifically one or more compounds having in their structure at least one alkyl-phenol group.

[0183]

[0176] This means that this compound or these compounds have in their formula at least one phenolic ring (i.e., a benzene ring substituted by one or more hydroxyl groups -OH) substituted by one or more alkyl groups.

[0177] According to a first embodiment, the additive(s) (iii) may be chosen from compounds (iii)1) comprising one or two phenolic ring(s) substituted by one or more alkyl groups chosen from methyl and β-butyl (or β-butyl) groups.

[0184]

[0178] These compounds (iii)1) may more particularly be selected from methyl-t-butyl phenols, dimethyl-t-butyl phenols, ethyl-t-butyl phenols, t-butyl phenols, di-t-butyl phenols, tri-t-butyl phenols, di-t-butyl-di-methyl phenols, and mixtures thereof.

[0185]

[0179] Preferred compounds are selected from 2,6-di-t-butyl-4-methylphenol (BHT), 4,6-di-tert-butyl-2-methylphenol, t-butyl hydroquinone (TBHQ), 2,6 and 2,4 di-t-butyl phenol, 2,4-dimethyl-6-t-butyl phenol, 2,4,6-tri-t-butyl phenol, 2,3,6-trimethyl phenol, 2,4,6-trimethyl phenol, 4,4'-methylene bis (2,6-di-t-butyl phenol) (CAS No. 118-82-1), alone or in mixtures.

[0186]

[0180] Particularly preferred compounds are selected from (di)tert-butyl phenols, methyl-tert-butylphenols and di-methyl-tert-butylphenols, their mixtures, and their pairwise condensation products, such as in particular 2,6-di-t-butyl-4-methyl phenol (BHT), 2,4-dimethyl-6-t-butyl phenol, 2,5-dimethyl-4-t-butyl phenol, 2,6 and 2,4 di-t-butyl phenol, 2,4,6-tri-t-butyl phenol, their mixtures, and their pairwise condensation products.

[0187]

[0181] According to a second embodiment, the additive(s) (iii) may be chosen from among the modified alkylphenol-aldehyde resins (iii)2) that can be obtained by Mannich reaction of an alkylphenol-aldehyde condensation resin:

[0188]

[0182] • with at least one aldehyde and / or ketone having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms;

[0189]

[0183] • and at least one hydrocarbon compound having at least one alkylpolyamine group, having between 1 and 30 carbon atoms, preferably between 4 and 30 carbon atoms,

[0190]

[0184] said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation:

[0191]

[0185] • of at least one alkylphenol substituted by at least one alkyl group, linear or branched, having from 1 to 30 carbon atoms, preferably a monoalkylphenol,

[0192]

[0186] • with at least one aldehyde and / or ketone having from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms.

[0193]

[0187] The alkylphenol-aldehyde condensation resin can be chosen from any resin of this type already known and in particular, those described in documents EP857776, EP1584673.

[0194]

[0188] The modified alkylphenol-aldehyde resins according to the invention can advantageously be obtained from at least one alkylphenol substituted at the para position. Nonylphenol is preferably used.

[0195]

[0189] The average number of phenolic nuclei per molecule of nonylphenol-aldehyde resin may advantageously be in the range of 6 to 25, preferably 8 to 17, and more preferably 9 to 16.

[0196]

[0190] The number of phenolic nuclei can be determined by nuclear magnetic resonance (NMR) or gel permeation chromatography (GPC).

[0191] Advantageously, the modified alkylphenol-aldehyde resins can be obtained by using the same aldehyde or ketone in both stages of its preparation.

[0197]

[0192] Modified alkylphenol-aldehyde resins can be obtained from at least one aldehyde and / or one ketone selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, and / or acetone. Preferably, the modified alkylphenol-aldehyde resin is obtained from at least one aldehyde, preferably at least formaldehyde (or methanal).

[0198]

[0193] Preferably, the modified alkylphenol-aldehyde resins are likely to be obtained from p-nonylphenol, formaldehyde and at least one hydrocarbon compound comprising at least one alkylpolyamine group.

[0199]

[0194] Said hydrocarbon compound may be an alkylpolyamine having at least two primary and / or secondary amine groups. In particular, the alkylpolyamine is advantageously chosen from primary or secondary polyamines substituted by, respectively, one or two alkyl groups comprising, preferably, from 12 to 24 carbon atoms, more preferably from 12 to 22 carbon atoms.

[0200]

[0195] Preferably, the modified alkylphenol-aldehyde resin is obtained from at least one alkylpolyamine having at least two primary amine groups, preferably three primary amine groups.

[0201]

[0196] In particular, the modified alkylphenol-aldehyde resin can advantageously be obtained from at least one alkylpolyamine in which all the amine groups are primary amines.

[0202]

[0197] Preferably, the modified alkylphenol-aldehyde resin is obtained from at least one alkylpolyamine comprising at least one fatty chain having 12 to 24 carbon atoms, preferably 12 to 22 carbon atoms.

[0203]

[0198] A particularly preferred alkylpolyamine is tallow dipropylenetriamine.

[0204]

[0199] Commercial alkylpolyamines are generally not pure compounds but mixtures. Among the suitable commercial alkylpolyamines, one can cite in particular the fatty-chain alkylpolyamines marketed under the names Trinoram®, Duomeen®, Dinoram®, Triameen®, Armeen®, Polyram®, Lilamin® and Cemulcat®.

[0205]

[0200] A preferred example is Trinoram®S, which is a tallow dipropylenetriamine, also known as N-(Tallowalkyl)dipropylenetriamine (CAS 61791-57-9).

[0206]

[0201] It is of course possible to combine the two embodiments and to use a combination of compounds (iii)1) and (iii)2) as described above.

[0207]

[0202] Thus, according to a preferred embodiment, the additive composition may comprise one or more compounds (iii)1) comprising one or two phenolic ring(s) substituted by one or more alkyl groups selected from the methyl and t-butyl groups, and one or more modified alkylphenol-aldehyde resins (iii)2).

[0208]

[0203] Preferably, the total content of antioxidant additive(s) (iii) in the composition is from 5 to 1000 ppm by mass, preferably from 5 to 500 ppm by mass, more preferably from 10 to 300 ppm by mass, relative to the sum of the masses of components (a) and (b).

[0209]

[0204] Lubricating additive (iv)

[0205] As a lubricating additive (iv), also called a friction modifying additive, the invention implements one or more additives, preferably chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol esters such as glycerol monooleate alone or in mixture with other glycerol esters, and mono- and polycyclic carboxylic acid derivatives.

[0210]

[0206] Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.

[0211]

[0207] Preferably, the total content of lubricant additive(s) (iv) in the composition is from 5 to 5,000 ppm by weight, preferably from 5 to 2,000 ppm by weight, and even better from 10 to 1,000 ppm by weight, relative to the sum of the masses of components (a) and (b).

[0212]

[0208] Other additives

[0213]

[0209] The marine fuel composition may also include other additives, in addition to the (i) cetane number improving additives described above, the (ii) deposit reducing additive(s) described above, and optionally the (iii) antioxidant and / or (iv) lubrication additives previously described.

[0214]

[0210] This or these other additives may be selected, for example, in a non-limiting manner, from among anti-corrosion additives, dispersing additives, demulsifying additives, anti-foaming agents, biocides, reodorants, combustion aids (catalytic combustion and soot promoters), cold-weather additives and in particular agents improving cloud point, pour point, LFT (limiting filterability temperature), anti-sedimentation agents, anti-wear agents, tracers, carrier solvents / oils and conductivity modifying agents.

[0215]

[0211] Examples of these additives include:

[0216]

[0212] a) antifoaming additives, including (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590;

[0217]

[0213] b) Cold Flow Improver (CFI) additives selected from ethylene and unsaturated ester copolymers, such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate copolymers described, for example, in documents US3048479, US3627838, US3790359, US3961961 and EP261957;

[0218]

[0214] c) cloud point additives, including (but not limited to) those selected from the group consisting of long-chain olefin / (meth)acrylic / maleimide ester terpolymers and fumaric / maleic acid ester polymers. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP112195, EP172758, EP271385, EP291367;

[0219]

[0215] e) polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate-based polymers as described in EP573490;

[0220]

[0216] f) anti-corrosion additives such as, for example, fatty acid ester dimers and aminotriazoles.

[0217] These additional additives may be present in quantities ranging, for each, from 5 to 1,000 ppm (each), preferably from 50 to 500 ppm by mass, relative to the sum of the masses of components a and b.

[0221]

[0218] The composition of additives may advantageously include an organic solvent, which may, for example, be chosen from aromatic hydrocarbon solvents such as the solvent marketed under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, including hydrotreated vegetable oils known as HVO, alone or in mixture.

[0222]

[0219] According to a preferred embodiment, the additive composition may include at least one solvent selected from alcohols. Particularly advantageously, the additive composition contains at least one monoalcohol in the C1 to C8 range, preferably selected from ethanol and ethyl-2-hexanol.

[0223]

[0220] Composition for marine fuel

[0224]

[0221] The composition according to the invention can be used as a base for manufacturing marine fuel or forming marine fuel. Marine fuel is understood to mean fuel having specifications suitable for use in ship diesel engines and boilers, prior to any conventional onboard treatment (sedimentation, centrifugation, filtration) before use. This type of fuel can also be used in stationary diesel engines of the same or similar type to those used for marine applications. It can be marine diesel and marine residual fuel.

[0225]

[0222] The composition according to the invention can in particular comply with all the specifications of marine fuels presented in the standard ISO 8217-June 2024, except for the conformity of the renewable base to the standard EN 14214, the CNSL not falling within clause 5 of the standard ISO 8217-June 2024.

[0226]

[0223] The composition according to the invention may in particular meet all the specifications required for one of the categories of fuels described in tables 1 to 4 of ISO 8217-June 2024.

[0227]

[0224] The marine fuel composition according to the invention contains from 65 to 99% by mass of the first component (a), from 1 to 35% by mass of the second component (b), and from 500 to 5000 ppm by mass of the composition (c) of additives relative to the sum of the masses of components a and b.

[0228]

[0225] The proportions of the different constituents, and in particular of components (a) and (b), can be adjusted so that the composition has:

[0229]

[0226] - a sulfur content of no more than 5000 mg / kg, and / or

[0230]

[0227] - a flash point of at least 60 °C, and / or

[0231]

[0228] - an acid value of not more than 0.5 mg KOH / g, in particular when component (a) comprises a distillate-type fossil base; or an acid value of not more than 2.5 mg KOH / g, in particular when component (a) comprises a residue-type fossil base.

[0232]

[0229] These contents are given in relation to the sum of the masses of components (a) and (b). Typically, the sum of the contents of the first and second components is thus equal to 100%. Furthermore, the composition may consist solely of the first and second components, and the composition of additives, without any other component.

[0233]

[0230] Other characteristics of the composition according to the invention such as its viscosity and density can also be adjusted by varying the proportions of components (a) and (b) of the composition.

[0234]

[0231] The composition may contain, in particular only, the first component in a content of 65 to 90% by mass, the second component in a content of 10 to 35% by mass, and the composition (c) of additives in a content of 1000 to 5000 ppm by mass, preferably 1500 to 4500 ppm, relative to the sum of the masses of components (a) and (b).

[0235]

[0232] Preferably, the composition may contain, in particular only, the first component in a content of 65 to 85% by mass, the second component in a content of 15 to 35% by mass, and the composition of additives in a content of 1000 to 5000 ppm by mass, preferably 1500 to 4500 ppm, relative to the sum of the masses of components (a) and (b).

[0236]

[0233] The composition according to the invention can be obtained by simple mixing of the first and second components and the composition of additives, or even additional additives, previously described.

[0237]

[0234] To facilitate their mixing, components (a) and (b), or at least the first component (a), may be preheated, for example to a temperature that lowers their viscosity. A person skilled in the art will be able to determine an appropriate preheating temperature.

[0238]

[0235] The addition of composition (c) of additives according to the invention makes it possible to significantly improve the cetane number, and in particular the estimated cetane number (ECN determined according to standard IP501), even with low levels of additives.

[0239]

[0236] The marine fuel composition according to the invention may in particular have one or more of the following characteristics:

[0240]

[0237] a sulfur content less than or equal to 0.5% by mass, for example from 0.05 to 0.5% by mass,

[0241]

[0238] - a density at 15 °C of at most 1010 kg / m³ 3 , of at most 991 kg / m 3 , of at most 975 kg / m3 , of a maximum of 960 kg / m 3 , of at most 920 kg / m 3 , of a maximum of 900 kg / m 3 or at most 890 kg / m 3 , in particular greater than 900 kg / m 3 , or in any interval defined by two of these limits,

[0242]

[0239] - a pour point of at most 30 °C, at most 6 °C, at most 0 °C or at most -6 °C, in particular greater than -42 °C, or within any interval defined by two of these limits,

[0243]

[0240] - a kinematic viscosity at 50 °C of at most 700 mm 2 / s, at most 500 mm 2 / s, at most 380 mm² / s, at most 180 mm 2 / s, at most 80 mm 2 / s, at most 30 mm 2 / s or at most 10 mm 2 / s, in particular greater than 2 mm 2 / s,

[0244]

[0241] - a kinematic viscosity at 40 °C of at most 11 mm 2 / s, or at most 6 mm 2 / s, in particular greater than 2 mm 2 / s,

[0245]

[0242] - a flash point of at least 60 °C, and typically of at most 150 °C.

[0246]

[0243] The invention makes it possible, in particular, to formulate a marine fuel composition with a very low sulfur content (less than 0.50% sulfur by mass), comprising a renewable component, CNSL, and optionally an EMAG. Examples

[0247]

[0244] Other features and advantages of the invention will become apparent from the examples given, which are indicative but not limiting, and with reference to the following figures:

[0248]

[0245] [Fig. 1] Figure 1 is a graph showing the ECN values ​​as a function of the additivation rate (curve with crosses) and the EMAG content (curve with circles) tested in Example 3.

[0249]

[0246] [Fig 2] Figure 2 is a comparative graph showing the impact of adding an additive composition according to the invention in the context of Example 2. This figure thus shows the impact of adding additives on ignition quality. Columns 0 to 5 correspond respectively to the mixture without additive, then to the mixtures with additive 1, additive 2, additive 3, additive 4 and additive 5.

[0250]

[0247] Example 1

[0251]

[0248] Several compositions were created using:

[0252]

[0249] - a VLSFO or a DML (distillate) as a component (a)

[0253]

[0250] - an EMAG

[0254]

[0251] - a CNSL as a component (b)

[0255]

[0252] The properties of VLSFO, DML and EMAG are summarized in Table 1. Table 2 summarizes the physicochemical characteristics of CNSL and Table 3 its elemental analysis.

[0256]

[0253] [Table 1] Properties of VLSFO, DML and EMAG.

[0257]

[0258]

[0254] NM = Not Measured

[0259]

[0255] * measurement carried out on the 10% residue after distillation

[0260]

[0256] [Table 2]

[0261]

[0262]

[0257] **NM = Not Measured - no more product

[0263]

[0258] [Table 3]

[0264]

[0265]

[0259] The characteristics of the VLSFO / CNSL and DML / CNSL mixtures are reported in Table 4.

[0266]

[0260] The characteristics of the VLSFO / CNSL / EMAG and DML / CNSL / EMAG mixtures are reported in Table 5.

[0267]

[0261] [Table 4] Analysis of mixtures according to tables 1 and 3 of ISO 8217:2024

[0268]

[0269]

[0262] [Table 5] Analyses of mixtures with CNSL and EMAG according to ISO Table 3

[0270] 8217:2024

[0271]

[0263] Example 2: Effect of additives on a VLSFO-CNSL mixture

[0272]

[0264] Various types of additives were added to the composition comprising 70% by mass of VLSFO and 30% by mass of CNSL of Example 1, the characteristics of which are detailed in Table 4 (composition noted RF180).

[0273]

[0265] Additive 1 is a cetane-enhancing additive: 2-EHN,

[0274]

[0266] Additive 2 is a deposit-reducing additive (detergent) of the type described in application EP4157971,

[0275]

[0267] Additive 3 is a mixture of additives 1 and 2,

[0268] Additive 4 corresponds to additive 3 to which a lubrication additive has been added, which is a mixture of glycerol esters,

[0276]

[0269] Additive 5 corresponds to additive 3 to which a phenolic antioxidant additive has been added.

[0277]

[0270] Table 6 lists the quantities of additives added to the composition.

[0271] [Table 6]

[0278]

[0272] Figure 2 shows the impact of the additives on the ECN of the tested composition. Figure 2 shows that additives 1 and 2, used in isolation, have no impact on the cetane number (ECN) of the composition, and additive 2 even has a negative impact. However, when these additives are combined (additive 3), the ECN of the composition increases significantly. Figure 2 also shows a synergistic effect when these additives are combined with a lubricant additive (additive 4) or an antioxidant additive (additive 5).

[0279]

[0273] Example 3: Addition of a composition of additives according to the invention

[0280]

[0274] 1000 ppm to 4000 ppm of an additive composition were added to the composition comprising 70% by mass of VLSFO and 30% by mass of CNSL of Example 1, the characteristics of which are detailed in Table 4 (composition denoted RF180). The tested additive composition, denoted CAdd, comprises a mixture of a cetane number improving additive (an alkyl nitrate), deposition reducing additives (as described in EP4157971), and phenolic antioxidant additives in relative amounts consistent with those of the additive composition of the present invention.

[0281]

[0275] Table 7 lists the ECN values ​​(measured according to IP 541 standard)

[0282]

[0276] [Table 7]

[0283]

[0277] A notable increase in ECN is observed from 1000 ppm of the added additive composition.

[0284]

[0278] This same composition of additives has been added to various VLSFO / CNSL / EMAG mixtures, in which the CNSL content is maintained at 30% by mass, with the added EMAG replacing the VLSFO.

[0285]

[0279] Figure 1 shows the measured ECN for compositions with and without EMAG. This figure demonstrates that if an ECN greater than 30 is targeted, a quantity of 1000 ppm of the additive composition is equivalent to substituting 20% ​​by mass of VLSFO with EMAG. This can make it possible to obtain a marine fuel composition that meets the specifications and the ECN target when the availability of EMAG is insufficient and / or too costly.

Claims

DEMANDS 1. Composition for marine fuel comprising: 65 to 99% by mass of a first component (a) comprising a fossil base, this first component having a sulfur content of not more than 1.5% by mass, preferably not more than 1% by mass, more preferably not more than 0.7% by mass, and a flash point of at least 60 °C, 1 to 35% by mass of a second component (b) consisting of cashew nut shell liquid (CNSL), from 500 to 5000 ppm by mass of a composition (c) of additives relative to the sum of the masses of components (a) and (b), said composition (c) of additives comprising: (i) one or more additives improving the cetane number, (ii) one or more deposit-reducing additives.

2. Composition according to claim 1, wherein the mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (ii) is 1:4 to 4:1, preferably 1:3 to 3:

1.

3. Composition according to claim 1 or 2, wherein the cetane number improving additive(s) (i) are selected from alkyl nitrates, aryl peroxides and alkyl peroxides, and preferably from alkyl nitrates of formula R-NO3, with R an alkyl radical comprising 2 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and even better the additive (i) is 2-ethylhexyl nitrate.

4. Composition according to any one of claims 1 to 3, wherein the deposit reducing additive(s) (ii) are selected from (ii)(1) quaternary ammonium salts other than betaines, (ii)(2) amido alkyl betaines, (ii)(3) non-quaternary polyisobutylene succinimides, and mixtures thereof, in particular from (ii)(1) quaternary ammonium salts other than betaines and (ii)(2) amido alkyl betaines.

5. Composition according to claim 4, wherein the deposit reducing additive(s) (ii) are selected from (ii)(1) quaternary ammonium salts other than betaines and (ii)(2) amido alkyl betaines, and optionally the mass ratio of the amount of the first additive (ii)(1) to the amount of the second additive (ii)(2) is in the range of 1:5 to 5:1, preferably 1:4 to 4:

1.

6. A composition according to claim 4 or 5, wherein: quaternary ammonium salts other than betaines are obtained by reaction with a quaternizing agent of a nitrogen compound comprising a tertiary amine function, this compound being the product of the reaction of an acylation agent substituted with a hydrocarbon group and a compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines, and alcohols, and optionally the acylation agent substituted with a hydrocarbon group is selected from mono- or polycarboxylic acids and their derivatives, in particular their ester derivatives, amides, or anhydrides, and preferably the acylation agent is selected from succinic, phthalic, and propionic acids and the corresponding anhydrides, and preferably The acylation agent substituted by a hydrocarbon group is a polyisobutenyl-succinic anhydride; the amido alkyl betaines have the following formula (III): in which R1 is a C1 to C34 hydrocarbon chain, linear or branched, R2 is a hydrogen atom or a hydrocarbon chain with C1 to C15 atoms. R3 is a hydrocarbon chain with C1 to C15 atoms, and R4 and R5 are identical or different and chosen independently of each other from a hydrogen atom and a hydrocarbon chain in C1 to C10, preferably in C1 to C6, it being understood that the groups R4 and R5 may contain one or more nitrogen groups and / or may be linked together to form one or more rings.

7. A composition according to any one of claims 1 to 6, wherein the composition of additives further comprises: (iii) one or more antioxidant additives chosen from compounds having in their structure at least one alkyl-phenol group, and optionally the mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (iii) is in the range of 60:1 to 1:

1.

8. Composition according to claim 7, wherein the antioxidant additive(s) (iii) are selected from: (iii)1) compounds comprising one or two phenolic nuclei substituted by one or more alkyl groups selected from methyl and t-butyl groups; preferably from methyl-t-butyl phenols, dimethyl-t-butyl phenols, ethyl-t-butyl phenols, t-butyl phenols, di-t-butyl phenols, tri-t-butyl phenols, di-t-butyl-dimethyl phenols, and mixtures thereof, and / or, (iii)2) modified alkylphenol-aldehyde resins that can be obtained by Mannich reaction of an alkylphenol-aldehyde condensation resin: • with at least one aldehyde and / or ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; • and at least one hydrocarbon compound having at least one alkylpolyamine group, having between 1 and 30 carbon atoms, preferably between 4 and 30 carbon atoms, said alkylphenol-aldehyde condensation resin being itself capable of being obtained by condensation: • of at least one alkylphenol substituted by at least one alkyl group, linear or branched, having from 1 to 30 carbon atoms, preferably a monoalkylphenol, • with at least one aldehyde and / or ketone having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

9. A composition according to any one of claims 1 to 8, wherein the composition of additives further comprises: (iv) one or more lubrication additives or anti-wear agents, and optionally the mass ratio of the quantity of additive(s) (ii) to the quantity of additives (iv) is in the range of 30:1 to 1:1, preferably 10:1 to 1:

1.

10. Composition according to claim 9, wherein the lubricant additive(s) or anti-wear agent(s) (iv) are selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol esters, and mono- and polycyclic carboxylic acid derivatives.

11. Composition according to any one of claims 1 to 10 wherein the first component comprises a fossil base selected from an atmospheric distillate, a vacuum distillate, an atmospheric residue, a vacuum residue and a viscoreduction residue; and optionally at least one fluxant of petroleum origin or of renewable origin.

12. Composition according to any one of claims 1 to 11 wherein the second component has an acid value of 0.1 to 20 mg KOH / g, preferably 0.1 to 10 mg KOH / g.

13. A process for manufacturing a marine fuel composition in which said composition results from mixing: 65 to 99% by mass of a first component (a) comprising a fossil base, this first component having a sulfur content of not more than 1.5% by mass, preferably not more than 1% by mass, more preferably not more than 0.7% by mass, and a flash point of at least 60 °C, 1 to 35% by mass of a second component (b) consisting of cashew nut shell liquid (CNSL), and 500 to 5000 ppm by mass of a composition (c) of additives relative to the sum of the masses of components (a) and (b), said composition (c) of additives comprising: (i) one or more additives improving the cetane number, (ii) one or more deposit-reducing additives.

14. A process according to claim 13, comprising at least one of the following features: the cetane number-improving additive(s) (i) are selected from alkyl nitrates and aryl or alkyl peroxides, and preferably from alkyl nitrates of formula R-NO3, with R an alkyl radical comprising 2 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and preferably the additive (i) is ethylhexyl nitrate; the deposit-reducing additive(s) (ii) are selected from (ii)(1) quaternary ammonium salts other than betaines, (ii)(2) amidoalkyl betaines, (ii)(3) the non-quaternary polyisobutylene succinimides, and mixtures thereof, in particular from (ii)(1) quaternary ammonium salts other than betaines and (ii)(2) amido alkyl betaines, the deposit reducing additive(s) (ii) are selected from (ii)(1) quaternary ammonium salts other than betaines and (ii)(2) amido alkyl betaines, and optionally the mass ratio of the quantity of the first additive (ii)(1) to the quantity of the second additive (ii)(2) is in the range of 1:5 to 5:1, preferably 1:4 to 4:

1.

15. A method according to claim 13 or 14, wherein the following are further added: (iii) one or more antioxidant additives, and the mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (iii) is within the range of 60:1 to 1:1, preferably 30:1 to 1:1, and / or (iv) one or more lubrication additives or anti-wear agents, and the mass ratio of the quantity of additive(s) (ii) to the quantity of additive(s) (iv) is in the range of 30:1 to 1:1, preferably 10:1 to 1:

1.

16. Use of an additive composition to improve the cetane number of a mixture containing 65 to 99% by mass of a first component (a) comprising a fossil base and having a sulfur content of not more than 1.5% by mass, preferably not more than 1% by mass, more preferably not more than 0.7% by mass, and a flash point of at least 60 °C, and 1 to 35% by mass of a second component (b) consisting of cashew nut shell liquid (CNSL), said additive composition comprising: (i) one or more additives improving the cetane number, (ii) one or more deposit-reducing additives, and being added to the mixture in an amount of 500 to 5000 ppm by mass.

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