MARINE FUEL COMPOSITE COMPRISING TIRE OIL AND A RENEWABLE SOURCE COMPONENT

Abstract

The invention relates to a marine fuel composition comprising: (i) 30 to 90% by mass of a first component comprising at least one 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 0.5% by mass, and a flash point of at least 60°C; (ii) 1 to 30% by mass of a second component consisting of tire oil and having a sulfur content of 0 to 1.5% by mass and a flash point of at least 40°C; (iii) 5 to 69% by mass of a third component consisting of alkyl esters of fatty acids of renewable origin, in proportions such that said composition has a sulfur content of not more than 0.5% by mass and a flash point of at least 60°C. Abstract figure: Figure 4

Description

Title of the invention: MARINE FUEL COMPOSITION COMPRISING TIRE OIL AND A COMPONENT OF RENEWABLE ORIGIN technical field

[0001] The present invention relates to a marine fuel composition comprising tire oil and a renewable component of the alkyl ester type derived from fatty acids of vegetable or animal origin. The addition of this renewable component makes it possible to limit black carbon emissions during combustion. Prior art

[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 also of fossil origin.

[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 and coastal areas.

[0004] The applicant described in document WO2023 / 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.

[0005] Furthermore, there is an important need, also encouraged by regulations, to limit tire waste in landfills and to recycle it.

[0006] One possible way to recycle tires is to obtain tire oil by pyrolysis. Document WO2020 / 021104A1 describes the use of tire oils as a base for marine fuel.

[0007] However, tire oil has a high content of aromatic compounds that can produce carbon black (“black carbon” or “BC” in Anglo-Saxon terminology) during combustion.

[0008] The BC is defined by Bond, TC et al. (2013), Bounding the role of black carbon in the climate System: A scientific assessment. Journal of Geophysical Research: Atmospheres, 118(11), 5380-5552. http: / / dx.doi.org / 10.1002 / jgrd.50171, as a distinct type of carbonaceous material, which forms primarily in flames, is directly emitted into the atmosphere, and exhibits a unique combination of physical properties. Two properties in particular have been found useful for measurement purposes:

[0009] - BC strongly absorbs visible light, with an absorption coefficient of mass (MAC) greater than 5 m2g 1 at a wavelength of 550 nm for freshly produced particles,

[0010] - BC is refractory, with a volatilization temperature close to 4000 K.

[0011] The International Maritime Organization (IMO) formally accepted the definition of Bond et al. (2013) in 2015.

[0012] From a climate perspective, carbon dioxide (CO2) emissions from marine fuels are of particular concern in the Arctic, where CO2 deposition on snow and ice reduces albedo, thereby promoting warming and melting. In addition to its effects on the climate, exposure to CO2 emissions has been associated with adverse effects on human health, including cardiopulmonary diseases, respiratory illnesses, and lung cancer. Reducing CO2 emissions is therefore desirable to mitigate these climate and health effects.

[0013] The applicant discovered that adding alkyl esters of fatty acids to compositions comprising a fossil base and tire oil makes it possible to maintain, or even reduce, black carbon emissions, and thus to control / limit the pollution emitted during the combustion of the compositions. Description of the invention

[0014] The present invention thus aims to provide a marine fuel composition containing tire oil, with low black carbon emissions. Another objective of the present invention is to provide a marine fuel composition with a low sulfur content. Yet another objective is to provide a marine fuel composition with a renewable component and a recycled component, which can be used with current marine fuel logistics.

[0015] The invention relates to a marine fuel composition comprising: (i) 30 to 90% by mass of a first component comprising at least one 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 0.5% by mass, and a flash point of at least 60°C, (ii) 1 to 30% by mass of a second component consisting of tire oil and having a sulfur content of 0 to 1.5% by mass and a flash point of at least 40 (iii) 5 to 69% by mass of a third component consisting of alkyl esters of fatty acids of renewable origin, in proportions such that said composition has a sulfur content of no more than 0.5% by mass and a flash point of at least 60 °C.

[0016] The composition according to the invention has the advantage of emitting during its combustion a quantity of black carbon (measured by photoacoustic spectroscopy) less than or equal to the quantity of black carbon emitted by the combustion (under identical combustion conditions) of the first component, alone or in mixture with the second component.

[0017] Advantageously, the composition according to the invention may comprise, or be made up of: (i) 40 to 80% by mass, preferably 45 to 80% by mass, of the first component, (ii) 1 to 20% by mass, preferably 5 to 15% by mass, of the second component, (iii) 5 to 59% by mass, preferably 5 to 50% by mass, of the third component.

[0018] The composition according to the invention may include a kinematic viscosity at 50 °C of at least 2 mm2 / s.

[0019] The composition according to the invention may include a bio-based carbon content measured according to ASTM D6866-24 of at least 6% by mass, preferably at least 10% by mass, more preferably at least 20% by mass, even more preferably at least 22% by mass, and up to 70% by mass.

[0020] The first component used in the present invention may comprise, or be composed of, at least one fossil base selected from a distillate, such as an atmospheric distillate or a vacuum distillate, and a hydrocarbon residue, such as an atmospheric residue, a vacuum residue, or a visbreaking residue. Optionally, the first component may further comprise at least one petroleum-derived fluxing agent.

[0021] The second component in the present invention may comprise one or more of the following features: - an initial boiling point of 100 °C or higher, - a flash point of at least 50°C, preferably at least 55°C, - a sulfur content of 0.8 to 1.5% by mass, preferably 0.8 to 1.0% by mass, - a bio-based carbon content of 20 to 100% by mass (measured according to ASTM D6866-24, DIN 51637 (2014) or ASTM D7026).

[0022] The third component used in the present invention may consist of methyl esters, ethyl esters and / or propyl esters, alone or in mixture.

[0023] Advantageously, the composition according to the invention may further comprise from 500 to 5000 ppm by mass, preferably from 1000 to 5000 ppm by mass, of a composition of additives comprising, or consisting of: (i) one or more cetane number improving additives selected from alkyl nitrates, aryl peroxides and alkyl peroxides, (ii) one or more deposit-reducing additives selected from among the different quaternary ammonium salts of betaines and amido alkyl betaine, wherein the mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (ii) is in the range of 4:1 to 1:4 and optionally: (iii) one or more antioxidant additives selected from compounds having in their structure at least one alkyl-phenol group in which 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.

[0024] The invention also relates to a method for manufacturing a marine fuel composition in which the following are mixed: (i) 30 to 90% by mass of a first component comprising at least one 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 0.5% by mass and a flash point of not less than 60 °C, (ii) 1 to 30% by mass of a second component consisting of tyre oil and having a sulfur content of 0 to 1.5% by mass and a flash point of at least 40°C, and (iii) 5 to 69% by mass of a third component consisting of alkyl esters of fatty acids from renewable sources, in proportions such that said composition resulting from the mixture has a sulfur content of not more than 0.5% by mass and a flash point of at least 60 °C.

[0025] The process may include mixing: (i) 40 to 80% by mass, preferably 45 to 80% by mass, of the first component, (ii) 1 to 20% by mass, preferably 5 to 15% by mass, of the second component, (iii) 5 to 59% by mass, preferably 5 to 50% by mass, of the third component.

[0026] Advantageously, the mixture can be made in proportions such as the composition further includes a kinematic viscosity at 50 °C of at least 2 mm2 / s.

[0027] Advantageously, the first component may comprise, or be made up of, at least one fossil base selected from a distillate, such as an atmospheric distillate or a vacuum distillate, and a hydrocarbon residue, such as an atmospheric residue, a vacuum residue or a viscoreduction residue, and optionally at least one petroleum-derived fluxant.

[0028] Advantageously, the second component may comprise one or more of the following features: - an initial boiling point of 100 °C or higher, - a flash point of at least 50°C, preferably at least 55°C, - a sulfur content of 0.8 to 1.5% by mass, preferably 0.8 to 1.0% by mass, - a bio-based carbon content of 20 to 100% by mass measured according to ASTM D6866-24.

[0029] Advantageously, the third component may consist of methyl esters, ethyl esters and / or propyl esters, alone or in mixture.

[0030] The process may also include adding to the mixture, at a concentration of 500 to 5000 ppm by mass, preferably 1000 to 5000 ppm by mass, a composition of additives comprising: (i) one or more cetane number improving additives selected from alkyl nitrates, aryl peroxides and alkyl peroxides, (ii) one or more deposit-reducing additives selected from among the different quaternary ammonium salts of betaines and amido alkyl betaines, in which the mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (ii) is within the range of 4:1 to 1:4 and optionally: (iii) one or more antioxidant additives selected from compounds having in their structure at least one alkyl-phenol group in which 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.

[0031] The invention also relates to the use of a component consisting of alkyl esters of fatty acids of renewable origin to reduce carbon black emissions during the combustion of a mixture containing a first component comprising at least one fossil base and having a sulfur content of at most 1.5% by mass, preferably at most 1% by mass, more preferably at most 0.5% by mass, and a flash point of at least 60°C, and a second component consisting of tire oil having a sulfur content of 0 to 1.5% by mass and a flash point of at least 40°C, in which the following are mixed: (i) 30 to 90% by mass of the first component, (ii) 1 to 30% by mass of the second component, and (iii) 5 to 69% by mass of the component consisting of alkyl esters of fatty acids from renewable sources, in proportions such that the composition resulting from the mixture has a sulfur content of no more than 0.5% by mass and a flash point of at least 60°C.

[0032] In particular, the composition and / or each of the components may exhibit one or more of the characteristics described by reference to the composition or the process. Detailed description of the invention

[0033] 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.

[0034] The expressions % by weight and % by mass have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0035] Unless otherwise indicated, measurements given in parts per million (ppm) are expressed in mass.

[0036] Similarly, and unless explicitly stated otherwise, the standards mentioned in the rest of the description correspond to the standard in force on June 27, 2024.

[0037] An atmospheric distillate is obtained from the atmospheric distillation of crude oil.

[0038] A vacuum distillate is obtained from the vacuum distillation of an atmospheric residue or another petroleum-derived residue.

[0039] An atmospheric residue is obtained from the atmospheric distillation of crude oil (bottom of the atmospheric distillation column).

[0040] A vacuum residue is obtained from the vacuum distillation of an atmospheric residue (bottom of the vacuum distillation column).

[0041] 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".

[0042] 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 (version 2020) or ASTM D2887 for measuring the boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, and ASTM D7500, D86, or DI 160 for distillates.

[0043] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0044] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0045] 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 D5622-17 / D2504-88 (2015). The nitrogen content can be measured according to ASTM D4629-17. The sulfur content can be measured according to ISO 20846:2011.

[0046] The halogen content, including chlorine, bromine, fluorine, can be measured according to the standard: ASTM D7359-18.

[0047] The density at 15°C is measured according to ISO 12185: March 2024.

[0048] Viscosity here refers to kinematic viscosity, measured at 50°C or 100°C, for example according to ISO 3104 standard: Nov 2023.

[0049] The pour point is measured according to ISO 3016: Sept 2019.

[0050] Sulphur content can be measured according to ISO 8754 or ASTM D4294 or ASTM D2622-21.

[0051] The calculated carbon aromaticity index (CCAI) is calculated according to the Lewis equation (recalled in standard NF ISO 8217-2024).

[0052] The asphaltene content can be measured according to standard NF T60-115 (January 2020).

[0053] The flash point can be measured according to standard NF EN ISO2719 - June 2018.

[0054] By "boiling point at X% of product Y", denoted "TX", we mean in the sense of the invention the boiling point of the remaining part of product Y once X% by mass of the starting product has been evaporated.

[0055] 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.

[0056] First component

[0057] The first component comprises, or is made up of, one or more fossil bases. This first component is advantageously a first fossil component.

[0058] The term "fossil base" or "fossil-derived base" or "fossil component" means a base / component consisting solely of hydrocarbons derived from crude oil. In particular, the first component is not derived from shale oil.

[0059] 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%; preferably at most 1% by mass, more preferably at most 0.5% by mass, and a flash point of at least 60 °C, for example from 60 to 150 °C.

[0060] The first component (a) comprises, or is made up of, at least one fossil base selected from a distillate, such as an atmospheric distillate or a vacuum distillate, and a hydrocarbon residue, such as an atmospheric residue, a vacuum residue or a viscoreduction residue.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] In particular, a first component may be used that complies with the specifications for marine fuels in ISO 8217:2024, in particular complying with the specifications required for one of the categories of marine distillate (DMX, DMA, DMZ, DMB) or residual fuel for marine (RMA, RME, RMG, RMK) defined in that standard.

[0065] In a preferred embodiment, the first component complies with the specifications of a residual fuel of category RME, RMG or RMK of the ISO 8217:2024 standard.

[0066] Advantageously, the fossil base of the first component may exhibit one or more of the following characteristics: - a sulfur content of at most 1.5% w / w, preferably at most 1% w / w, or even at most 0.8% w / w or at most 0.8% w / w, and typically at least 0.01 or 0.05% w / w, - a density at 15 °C of 845 to 1060 kg / m3, - a viscosity at 100 °C of 10 to 2500 mm2 / s.

[0067] By way of example, a fossil base of the residue type includes: - heavy fuel oils or HFOs (in English "Heavy fuel oil"), - low density heavy fuel oils ("HFO low density"), - very low sulfur fuel oils or VLSFOs (in English "Very Low Sulfur Fuel Oil"), - Low sulfur and low viscosity heavy fuel oils or "VLSFO low viscosity".

[0068] A fossil base of distillate type includes marine diesels or MDO (in English “Marine Diesel oil”.

[0069] 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 and / or a viscosity at 100 °C of 20 to 2500 mm2 / s.

[0070] When the residue is a vacuum residue, it may exhibit at least one of the following characteristics:

[0071] 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,

[0072] regardless of the sulfur content, a Sa value greater than 0.75,

[0073] regardless of the sulfur content, a density at 15 °C of 950 to 1000 kg / m3,

[0074] regardless of the sulfur content, a viscosity at 100 °C of 20 to 2500 mm² / s,

[0075] regardless of the sulfur content, a viscosity at 50 °C of 150 to 600000 mm2 / s.

[0076] When the residue is a viscoreduction residue, it may have at least one of the following characteristics:

[0077] 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,

[0078] regardless of the sulfur content, a Sa value less than 0.75,

[0079] regardless of the sulfur content, a density at 15 °C of 950 to 1060 kg / m3,

[0080] regardless of the sulfur content, a viscosity at 100 °C of 80 to 1500 mm² / s,

[0081] regardless of the sulfur content, a viscosity at 50 °C of 1700 to 300000 mm2 / s.

[0082] 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, - a viscosity at 100 °C of 10 to 180 mm² / s, - a viscosity at 50 °C of 50 to 6200 mm2 / s.

[0083] In addition to at least one hydrocarbon residue and / or at least one distillate, the first component may further comprise at least one petroleum-derived fluxing agent.

[0084] This fluxing agent can be added in quantities enabling the desired sulfur content and / or desired flash point of the first component to be obtained.

[0085] This petroleum-based fluxing agent is, for example, chosen from: - diesel fuels derived from the direct distillation of petroleum: kerosene, lamp oil, light diesel, medium diesel, heavy diesel, - vacuum distillation products of atmospheric residue: light vacuum diesel, medium vacuum diesel, heavy vacuum diesel, distillate, - atmospheric or vacuum distillation products of effluents from conversion units: viscoreducing diesel, viscoreducing distillate, - 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, - products from steam cracking units: pyrolysis oil or gasoline.

[0086] Typically, the petroleum-derived flux content of the first component can be from 0 to 30% by mass, preferably from 0 to 21% by mass, the remainder consisting of at least one hydrocarbon residue and / or at least one distillate.

[0087] Second component consisting of tire oil

[0088] The expression "tire oil" refers to hydrocarbon liquid products obtained from the pyrolysis of tires, in particular used tires.

[0089] The second component is thus derived from tire recycling: it will be referred to as a recycled component. Tire oil also contains biogenic or bio-based carbon, that is, carbon derived from natural materials such as natural rubber; this second component therefore has a significant biogenic or bio-based carbon content.

[0090] Generally, the bio-based carbon content of a tire oil, measured according to ASTM D6866-24, DIN 51637 (2014) or ASTM D7026, is at least 20% by mass, with, for example, a bio-based carbon content of around 20-25% by mass for passenger car tires and 25-35% by mass for tires of agricultural vehicles or transport vehicles (buses, trucks, etc.). However, the bio-based carbon content of a tire oil can reach 100% by mass, particularly for tires made from synthetic rubber of renewable origin (for example, from butadiene produced from ethanol derived from biomass).

[0091] Tire oils contain, in particular, paraffins, i-paraffins (isoparaffins), dienes, alkynes, olefins, naphthenes, and aromatics. Tire oils also contain impurities containing heteroatoms, such as organic, oxygenated, sulfurous, nitrogenous, and / or silylated compounds, metals, salts, and phosphorus compounds.

[0092] The composition of a tire oil is essentially (in particular more than 80% by mass, most often more than 90% by mass) made up of hydrocarbons having from 1 to 150 carbon atoms and impurities.

[0093] A tire oil typically comprises 5 to 80% by mass of paraffins (including cycloparaffins), 10 to 95% by mass of unsaturated compounds (including olefins, dienes, and acetylenes), 15 to 80% by mass of aromatics, most often 20 to 80% by mass, or even 30 to 80% by mass of aromatics. These contents can be determined by gas chromatography.

[0094] A tire oil may have an initial boiling point of at least 15°C, typically from 15 to 150 °C; and a final boiling point of at most 800 °C, generally from 250 to 750 °C-800 °C (measured according to standard NF EN 15199-1 / 2), most often from 350 to 700 °C or from 350 to 600 °C.

[0095] A tire oil may comprise one or more of the following characteristics: - An aromatic compound content of 15 to 80% by mass, most often 20 to 80% by mass, or even 30 to 80% by mass, notably measured according to ASTM D6591, - Heteroatom content of 0 to 6% by mass, most often 0 to 3% by mass.

[0096] A tire oil may in particular comprise one or more of the following heteroatom contents: from 0 to 1.5% by mass of oxygen (measured according to ASTM D5622), from 1 ppm to 1.5% by mass of nitrogen (measured according to ASTM D5291), from 0 to 1.5% by mass of sulfur, most often from 0.8 to 1.5% by mass of sulfur (measured according to ASTM D2622), from 1 to 1000 ppm of metals (measured by ICP), from 50 to 100 ppm of chlorine (measured according to EN 14077), 1 to 100 ppm of silicon (measured by ICP).

[0097] The process according to the invention may thus include, in particular only, a step of supplying tire oil comprising: - a step of obtaining tire oil by pyrolysis, - an optional step of fractionating the obtained tire oil.

[0098] Advantageously, the supply step may include, in particular only, a preliminary step a1) of supplying used tires; a step a2) of pyrolyzing said used tires at a temperature of at least 300°C; a step a3) of recovering a pyrolysis effluent and separating a hydrocarbon fraction Cl to C4 of said pyrolysis effluent, the remaining liquid fraction being said tire oil, an optional step a5) of fractionating the tire oil.

[0099] The pyrolysis process should be understood as a thermal cracking process in the absence of air, typically carried out at a temperature of 300 to 1000 °C or 400 at 700 °C, implemented in the presence or absence of a catalyst and / or a gas (rapid pyrolysis, flash pyrolysis, catalytic pyrolysis, hydropyrolysis, steam pyrolysis, ...).

[0100] The fractionation step can be carried out by distillation, for example by distillation at atmospheric pressure or under reduced pressure, or by decantation.

[0101] Fractionation can be implemented to separate one or more of the following fractions:

[0102] (i) a naphtha fraction having a final boiling point of at most 150 °C, by For example, a temperature of 100 to 150 °C, and typically an initial boiling point of at least 15 °C.

[0103] (ii) a fraction having an initial boiling point of at least 100 °C, for example from 100 °C to 160 °C; and a final boiling point of at most 800 °C, generally from 250 to 800 °C or from 350 to 800 °C.

[0104] This last fraction may have one or more of the following characteristics: - a sulfur content of 0.8 to 1.5% by mass, preferably of 0.8 to 1.0% by mass, - an initial boiling point of 100 °C or more, in particular of 100 to 160 °C, - a flash point of at least 40 °C, preferably of at least 50 °C, more preferably of at least 55 °C, - a heteroatom content of at most 3% by mass, for example of 0 to 3% by mass.

[0105] Third component of alkyl esters

[0106] Alkyl esters of fatty acids are usually produced by the reaction of vegetable oils and / or animal fats with alcohols in the presence of a suitable catalyst. The reaction of oils / fats with an alcohol to produce a fatty acid ester and glycerin is known as transesterification. Alternatively, alkyl esters of fatty acids can be produced by the reaction of a fatty acid with an alcohol (esterification reaction) to form a fatty acid ester.

[0107] The third component is therefore exclusively of biological origin: we will speak of a component of renewable origin.

[0108] Vegetable oils may be selected from pine oil, rapeseed oil, sunflower oil, castor oil, peanut oil, linseed oil, babassu oil, hemp oil, linola oil, jatropha oil, peanut oil, rice bran oil, mustard oil, carinata oil, coconut oil, copra oil, olive oil, palm oil, cottonseed oil, corn oil, palm kernel oil, soybean oil, pumpkin seed oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, tung oil, rice oil, safflower oil, oil algae, used oils, and any combination thereof.

[0109] Used oils include used cooking oils (used food oils) and oils recovered from wastewater, such as grease / trap and drain oils, gutter oils, sewage oils, for example from wastewater treatment plants, and used grease from the food industry.

[0110] Animal fats may be chosen from tallow, lard, fat (yellow and brown fat), fish oils / fats, milk fat and any combination thereof.

[0111] The alcohol used to manufacture the alkyl esters of the present invention can be chosen from linear or branched, aliphatic or aromatic, primary, secondary or tertiary alcohols, and can have a number of carbons from 1 to 22. Advantageously, the alcohol can be chosen from methanol, ethanol, propanol and mixtures thereof, preferably from methanol, ethanol, and mixtures thereof.

[0112] In a preferred embodiment, the alkyl ester component comprises, or is made up of, methyl esters, ethyl esters, propyl esters, alone or in mixture, preferably methyl esters, ethyl esters, alone or in mixture, for example methyl esters. In a preferred embodiment, the alkyl ester component thus 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.

[0113] Composition of additives

[0114] The marine fuel composition of the present invention may further include a composition of additives to improve the ignition and combustion qualities of the composition.

[0115] This composition of additives comprises: (i) one or more cetane number improving additives selected from alkyl nitrates, aryl peroxides and alkyl peroxides, (ii) one or more deposit-reducing additives selected from among the different quaternary ammonium salts of betaines and amido alkyl betaines. The mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (ii) is in the range of 4:1 to 1:4, preferably 3:1 to 1:3.

[0116] In a preferred embodiment, the additive composition further comprises:

[0117] (iii) one or more antioxidant additive(s) selected from compounds having in their structure at least one alkyl-phenol group, with a mass ratio of the quantity of additive(s) (i) to the quantity of additive(s) (iii) in the range of 60:1 to 1:1, preferably 30:1 to 1:1.

[0118] Additive (i) improving the cetane number

[0119] The additive composition implements as additives (i) one or more cetane number improving additives, also known as procetane additives or cetane booster additives.

[0120] The additive(s) (i) may in particular be chosen from alkyl-nitrates and aryl or alkyl peroxides.

[0121] Among the aryl peroxides, benzyl peroxide is a notable example. Among the alkyl peroxides, tert-butyl peroxide is a notable example.

[0122] The additive(s) (i) are preferably chosen from alkyl-nitrates, and more preferably those of formula R-NO3 with R an alkyl radical comprising from 2 to 12 carbon atoms, preferably from 4 to 8 carbon atoms.

[0123] A particularly preferred additive (i) is ethyl hexyl nitrate.

[0124] Preferably, the total content of cetane number improving additive(s) (i) in the composition is from 5 to 5,000 ppm by mass, preferably from 5 to 1,000 ppm by mass, more preferably from 10 to 500 ppm by mass, relative to the total mass of the marine fuel composition.

[0125] Additives (ii) deposit reducer

[0126] The additive composition used further comprises one or more detergent additive(s) (ii), also referred to as deposit-reducing additive(s), selected from quaternary ammonium salts other than betaines and amido alkyl betaines.

[0127] In a preferred embodiment, additives (i) will be used at least one first additive (i)(1) selected from the different quaternary ammonium salts of betaines, as previously described, and at least one second additive (i)(2) selected from the amido alkyl betaines, as previously described, the mass ratio of the quantity of the first additive (i)(1) to the quantity of the second additive (i)(2) being in the range of 1:5 to 5:1, preferably 1:4 to 4:1.

[0128] For example, the additives described in patent EP4157971B1 filed by the applicant and defined below may be used.

[0129] Preferably, the total content of deposit-reducing additive(s) (ii) in the composition is 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 total mass of the marine fuel composition.

[0130] (i)(l) Quaternary ammonium salts

[0131] 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.

[0132] In a second embodiment, the quaternary ammonium salt is chosen from quaternized PIBA (polyisobutylene-amine) compounds, or from quaternized polyether-amines.

[0133] According to the first embodiment, which is preferred, said nitrogen compound is the product of the reaction of an acylation agent substituted by 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.

[0134] 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.

[0135] 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.

[0136] In 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.

[0137] According to a particularly preferred embodiment, the acylation agent substituted by a hydrocarbon group is a polyisobutenyl-succinic anhydride (PIBSA).

[0138] 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):

[0139] [Chem.l] R6

[0140] [Chem.2]

[0141] in which:

[0142] 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;

[0143] X is an alkylene group having from 1 to 20 carbon atoms, preferably from 1 to 5 carbon atoms;

[0144] m is an integer between 1 and 5;

[0145] n is an integer between 0 and 20; and

[0146] R8 is a hydrogen atom or an alkyl group from Cl to C22.

[0147] 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).

[0148] 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.

[0149] The additive (i)(l) can advantageously be chosen from polyisobutylene succinimides functionalized by a quaternary ammonium group.

[0150] (i)(2) Amido alkyl betaines

[0151] Amido alkyl betaines are advantageously chosen from among the amido alkyl betaines, of the following formula (III):

[0152] [Chem.3]

[0153] in which:

[0154] RI is a linear or branched hydrocarbon chain in Cl to C34,

[0155] R2 is a hydrogen atom or a Cl-15 hydrocarbon chain

[0156] R3 is a hydrocarbon chain in Cl to C15, and

[0157] R4 and R5 are identical or different and chosen independently of each other from a hydrogen atom and a hydrocarbon chain in Cl to CIO, preferably in Cl 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.

[0158] In a preferred embodiment, the alkyl betaine amido of formula (III) may comprise one or more of the following features: - RI 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 hydrocarbon chain in the Cl to C8 range, preferably a hydrogen atom, - R3 is a hydrocarbon chain in C1 to C8, preferably in C2 to C4, - R4 and R5 are identical or different and chosen independently from each other from a hydrogen atom and a hydrocarbon chain in Cl 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.

[0159] The additive of formula (III) can be obtained by reaction:

[0160] (a) of a tertiary amine substituted by a hydrocarbon group selected from (C8-C30 alkyl) amidopropyldi(C1-C4 alkyl)amines and (C8-C30 alkenyl) amidopropyldi(C1-C4 alkyl)amines; preferably among the (C8-C30 alkyl) amidopropyldimethylamines and (C8-C30 alkenyl) amidopropyldimethylamines; preferably oleylamidopropyl dimethylamine with

[0161] (b) halogen-substituted acetic acid, or one of its salts, or one of its derivatives ester or amide; preferably sodium chloroacetate;

[0162] said reaction product being preferably devoid of non-covalent anionic species.

[0163] Preferably, compound (a) is oleylamidopropyl dimethylamine and compound (b) is sodium chloroacetate.

[0164] Additives (iii) antioxidant

[0165] The antioxidant additive (iii) is chosen from alkyl phenol compounds and more specifically one or more compound(s) having in their structure at least one alkyl-phenol group.

[0166] This means that this or these compounds have in their formula at least one phenolic nucleus (i.e. a benzene nucleus substituted by one or more hydroxy groups -OH) substituted by one or more alkyl groups.

[0167] According to a first embodiment, the additive(s) (iii) can be chosen from compounds (iii)l) comprising one or two phenolic ring(s) substituted by one or more alkyl groups chosen from methyl and t-butyl (or tert-butyl) groups.

[0168] These compounds (iii)l) 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.

[0169] 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.

[0170] 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.

[0171] 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: • 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,

[0172] 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 from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] The number of phenolic nuclei can be determined by nuclear magnetic resonance (NMR) or gel permeation chromatography (GPC).

[0177] Advantageously, the modified alkylphenol-aldehyde resins can be obtained by using the same aldehyde or ketone at both stages of its preparation.

[0178] 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).

[0179] 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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] A particularly preferred alkylpolyamine is tallow dipropylenetriamine.

[0185] Commercial alkylpolyamines are generally not pure compounds but mixtures. Among the commercially available alkylpolyamines that are suitable, we can mention in particular the fat-chain alkylpolyamines marketed under the names Trinoram®, Duomeen®, Dinoram®, Triameen®, Armeen®, Polyram®, Lilamin® and Cemulcat®.

[0186] A preferred example is Trinoram®S, which is a tallow dipropylenetriamine, also known as N-(Tallowalkyl)dipropylenetriamine (CAS 61791-57-9).

[0187] 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.

[0188] Thus, according to a preferred embodiment, the additive composition may comprise one or more compounds (iii)l) 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).

[0189] 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 total mass of the marine fuel composition.

[0190] Other additives

[0191] The additive 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) previously described antioxidant additives.

[0192] This or these other additives may, for example, be selected, without limitation, from among anti-corrosion additives, dispersant additives, demulsifying additives, anti-foaming agents, biocides, reodorants, combustion aids (catalytic combustion and soot promoters), cold-weather performance additives and including cloud point enhancers, pour point enhancers, filter plugging point enhancers, anti-sedimentation agents, anti-wear agents, tracers, solvents / carrier oils and conductivity modifying agents.

[0193] Examples of these additives include:

[0194] 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;

[0195] 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;

[0196] 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, FR2528423, EPI 12195, EP172758, EP271385, EP291367;

[0197] e) polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate-based polymers as described in EP573490;

[0198] f) anti-corrosion additives such as, for example, fatty acid ester dimers and aminotriazoles.

[0199] 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 total mass of the marine fuel composition.

[0200] Composition for marine fuel

[0201] 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.

[0202] The composition according to the invention can in particular meet all the specifications of marine fuels presented in the ISO 8217:2024 standard, except for the tire oil content.

[0203] The composition according to the invention may in particular comply with the specifications of DF or RF type fuels, as described respectively in Table 1 and in Table 3 and Clause 5 of ISO 8217:2024 (except for the incorporation of tire oil).

[0204] The marine fuel composition according to the invention contains from 30 to 90% by mass of the first component, to which is added from 1 to 30% by mass of the second component, and from 5 to 69% by mass of the third component. The proportions of the different constituents are adjusted so that the composition has a sulfur content of no more than 5000 mg / kg and a flash point of at least 60 °C.

[0205] These contents are given in relation to the total composition. Typically, the sum of the contents of the first, second, and third components is thus equal to 100%. In other words, the composition may consist solely of the first, second, and third components.

[0206] In one embodiment, the composition further comprises a composition of additives. In this case, the sum of the contents of the first component, second component, third component and the composition of additives is equal to 100%.

[0207] The addition of alkyl esters of fatty acids allows the composition to emit carbon black emissions during its combustion less than or equal to the carbon black emissions emitted during the combustion of the first component alone or in mixture with the second component, under the same combustion conditions.

[0208] Other characteristics of the composition according to the invention such as its viscosity and / or its density can also be adjusted by varying the proportions of the different components of the composition.

[0209] In one embodiment, the composition may contain, in particular only, the first component in a content of 40 to 80% by mass, the second component in a content of 1 to 20% by mass, and the third component in a content of 5 to 59% by mass, and optionally the composition of additives.

[0210] In a preferred embodiment, the composition may contain, in particular only, the first component in a content of 45 to 80% by mass, the second component in a content of 5 to 15% by mass, and the third component in a content of 5 to 50% by mass, and optionally the composition of additives.

[0211] In one embodiment, the composition may consist of: - of the first component in a content of 30 to 90% by mass, preferably 40 to 80% by mass, more preferably 45 to 80% by mass or 50 to 80% by mass, - of the second component in a content of 1 to 30% by mass, preferably 1 to 20% by mass, more preferably 5 to 15% by mass, - the remainder being made up of the third component, and optionally the composition of additives.

[0212] The content of the third component of the composition according to the invention, and in particular of methyl esters, can be determined by the test methods IP631 or ASTM D7963, as described in ISO 8217:2024.

[0213] The composition according to the invention can be obtained by simple mixing of the first, second and third components previously described, and optionally of the composition of additives.

[0214] To facilitate their mixing, the three components, most often at least the first component, or even the first and second components, 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.

[0215] The marine fuel composition according to the invention may in particular have one or more of the following characteristics: - a sulfur content less than or equal to 0.5% by mass, for example from 0.01 to 0.5% by mass, - a density at 15 °C of at most 1010 kg / m3, at most 991 kg / m3, at most 975 kg / m3, at most 960 kg / m3, at most 920 kg / m3, at most 900 kg / m3 or at most 890 kg / m3, in particular greater than 900 kg / m3, or within any interval defined by two of these limits, - 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, - a kinematic viscosity at 50 °C of at most 700 mm² / s, at most 500 mm² / s, at most 380 mm² / s, at most 180 mm² / s, at most 80 mm² / s, at most 30 mm² / s or at most 10 mm² / s, in particular greater than 2 mm² / s, - a flash point of at least 60°C.

[0216] The invention makes it possible in particular to formulate a composition for marine fuel with a very low sulfur content (less than 0.50% by mass of sulfur), comprising a renewable component and a recycled component.

[0217] The composition of the present invention typically comprises a bio-based carbon content, measured according to ASTM D6866-24, of at least 6% by mass, preferably at least 10% by mass, more preferably at least 20% by mass, and even more preferably at least 22% by mass. The maximum bio-based carbon content of the composition according to the invention can reach 70% by mass, most often 55% by mass, and probably at most 35% or 30% by mass. mass. Figures

[0218] 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:

[0219] [Fig-1] The [Fig. 1] represents the curves of engine load (circles) and cumulative fuel mass (triangles) as a function of time for the test sequence of Example 1.

[0220] [Fig.2] Fig.2 represents the weighted NOx emissions of fuels Example 1 in relation to the reference fuel MGO.

[0221] [Fig.3] Fig.3 represents the weighted carbon black emissions of fuels of example 1 compared to the reference fuel MGO.

[0222] [Fig.4] Fig.4 represents the estimated cetane number (ECN) for the compositions of example 3.

[0223] [Fig.5] Fig.5 represents the post-combustion period for the compositions of Example 3. Examples

[0224] Example 1 - Carbon black and NOx emissions

[0225] Carbon black and NOx emissions from three marine fuels were measured under the combustion conditions described below.

[0226] The engine test bench includes a 4-stroke diesel engine whose characteristics are shown in Table 1, and whose performance is shown in Table 2.

[0227] [Tables 1] Model: MAN 5L 16 / 24 Serial Number: 21881 Year of Manufacture: 2003 Cycle: 4-stroke Number of Cylinders: 5 Configuration: Inline Bore: 160mm Stroke: 240mm Compression Ratio: 15.5 Piston Speed: 8m / s Air Intake: Single-stage turbocharged Regulation: IMG Tier II

[0228] [Tables2] Speed ​​1000 rpm Rated power 450kW Alternator power 430kW Max consumption ~100kg / h Exhaust gas flow 3400kg / h Exhaust gas temperature 350°C Max cylinder pressure 170bar

[0229] In its normal use, the engine test bench is supplied with either MGO (Marine Gasoline) or VLSFO. These two fuels are stored in underground tanks and centrifuged before being sent to the engine.

[0230] MGO was used as a reference fuel during these tests, in particular to ensure the repeatability of emission measurements at the beginning and end of the campaign.

[0231] MGO is the reference fuel used for engine acceptance and against which pollutant emissions from any other fuel must be compared.

[0232] Carbon black emission measurements were carried out according to the test sequence in [Fig. 1], which shows engine load as a function of time (a stepped curve defined by circles) and the cumulative fuel consumption value as a function of time (a curve defined by triangles). The sampling point complies with the requirements of the applicable standards: NF X 44-052 (Sampling of dust in a gas stream), NF EN 13284-1 (Emissions from stationary sources - Determination of low mass concentrations of dust - Part 1: Manual gravimetric method), and EN 15259 (Air quality - Measurement of emissions from stationary sources - Requirements for measurement sections and sites and for the objective, plan and measurement report).

[0233] Carbon black emissions were measured using Photo Acoustic Sensor (PAS) technology on an AVL MSS483 device according to the following methodology: a modulated laser beam heats the black absorbing particles in the exhaust gases, producing a periodic pressure pulse detected by a microphone as an acoustic wave. The signal is then amplified and filtered to determine the soot concentration.

[0234] Three fuels were tested: a VLSFO (“Very low sulfur Fuel Oil”), a mixture of VLSFO and EMAG (B30) and a VLSFOZTPO / EMAG (TPO) mixture.

[0235] The components of the fuels tested are listed in Table 3.

[0236] [Tables3] Product VLSFO B30 VLSFO / TPO / EMAG Components Composition (% mass) Vacuum residue 411-605 70 70 62 Diesel base 411-598 30 Diesel base 411-729 8 EMAG 410-530 30 20 TPO 411-728 10

[0237] The elemental analysis of the tire oil used (TPO) is reported in Table 4. It is a 140+ fraction of a tire oil (noted as TPO 140+ in the tables), exhibiting a boiling range of 140 °C to 600 °C.

[0238] [Tables4] Analysis Unit Standard TPO 140+ Kinematic viscosity at 50 °C mm² / s ISO 3104 5.136 Kinematic viscosity at 100 °C mm² / s ISO 3104 1.797 Density at 15 °C kg / m³ ISO 12185 948.7 CCAI - - 883 VGC - ASTM D2501 0.93 Sulfur mg / kg ASTM D2622 9340 Water mg / kg NF ISO 3733 <0.05 Ash %m ISO 6245 0.003 Pensky-Martens flash point °C ISO 2719 59.5 Pour point °C ISO 3016 -18 Asphaltenes 0.3299 Xylene insolubles mg / kg <100 CCR Acid value %m mgKOH / g ISO 10370 ASTM D664 - TAN ASTM D664 - SAN 1.62 8.58 <0.05 Estimated Cetane Number (ECN) Lower Heating Value (LHV) MJ / kg IP541 ASTM D240 6.6 40.480 Copper Corrosion 3h at 100°C - ASTM DI30 IA S-Value S Sa So - ASTM D7157 0.97 0.26 0.72 TSE %m ISO 10307-1 0.02 TSP ISO10307-2A 0.01 TSA ISO10307-2B <0.01 Induction Period - Rapidoxy min EN 16091 modified 43.53 TAN = Total Acid Number SAN = Strong Acid Number

[0239] The elemental analysis of the fraction of tire oil used is reported in Table 5.

[0240] [Tables5] Analysis Unit Standard TPO 140 + Carbon Hydrogen Nitrogen Sulfur %m ASTM D5291 84.20 10.80 0.97 0.92 Oxygen %m ASTM D5622 0.90 Phosphorus Calcium Iron Sodium Nickel Vanadium Silicon Aluminum Zinc Chlorine mg / kg IP 501 6 <3 3 2 <1 <1 17 <5 5 <2 Organic Chlorine mg / kg EN14077 10

[0241] The characteristics of the fuels tested are summarized in Table 6. The analyses were carried out according to Tables 2 and 3 of ISO 8217:2024, Table 2 for VLSFO and Table 3 for bio-VLSFO.

[0242] [Tableauxô] Product VLSFO B30 VLSFO T PO EMA G Reference 411-834 Characteristics Unit Standard Analysis Kinematic viscosity at 50 °C mm² / s ISO 3104 72.08 95.20 55.69 Density at 15 °C kg / m³ ISO 12185 920.3 938.7 934.9 CCAI - - 801 816 820 Sulfur mg / kg ASTM D262 2 0.46 0.44 0.47 Pensky-Martens flash point °C ISO 2719 >67 >67 89.0 H₂S mg / kg IP 570 <0.60 <0.60 <0.60 Acid value mgKOH / g ASTM D664 0.11 0.22 1.31 CCR %m ISO 10370 7.48 8.06 6.99 Pour point °C ISO 3016 < 12 < 12 0 Water %m NF ISO 3733 0.02 0.03 0.05 Ash %m ISO 6245 0.031 0.021 0.008 Vanadium mg / kg IP 501 9 9 8 Sodium mg / kg IP 501 15 18 15 Aluminum + Silicon mg / kg IP 501 < 1 3 < 12 Used lubricating oil mg / kg IP 501 Ca = 3 Ca = 3 Ca = 3 TSP %m ISO 10307-1 0.01 0.01 0.01 TSA ISO 10307-2 A 0.02 0.03 0.01 TSE ISO 10307-2 B 0.01 0.01 0.01 EMAG content %m ASTM D796 3 0 30 20 Lower heating value MJ / kg ASTM D240 41.945 40.203 40.715 Estimated cetane number (ECN) - IP 541 41.1 39.0 36.4

[0243] Figure 2 shows that the NOx emissions of the VLSFO / TPO / EMAG mixture are lower than the NOx emissions of the reference fuel, MGO. The use of these bases, which are not derived from petroleum refining, complies with MARPOL regulations.

[0244] Fig. 3 shows that BC emissions from the VLSFO / TPO / EMAG mixture are from same order of magnitude as BC emissions from the VLSFO.

[0245] The addition of EMAG limits carbon black emissions. Thus, the degradation expected from the addition of TPO is mitigated by the presence of EMAG. The increase in NOx emissions from the VLSFO / TPO / EMAG mixture that could be expected due to the incorporation of TPO is, however, limited and allows compliance with MARPOL regulations. This is also evident from the analysis of Figures 4 and 5 of Example 3, which show that the combustion quality of a VLSFO / EMAG / TPO mixture is better (lower ABP) compared to VLSFO or to VLSFO / EMAG and VLSFO / TPO mixtures, despite degraded ignition quality.

[0246] Example 2 - marine fuel composition

[0247] The same fraction of tire pyrolysis oil was mixed with another VLSFO and an EMAG, or with a distillate (DMA) and an EMAG.

[0248] The characteristics of VLSFO, distillate and EMAG are shown in Tables 7, 8 and 9 respectively.

[0249] Table 7 sets out the characteristics of VLSFO in accordance with the specifications described in Table 2 of 1TSO 8217:2024. Table 8 sets out the characteristics of Distillate (DMA) in accordance with the specifications described in Table 1 of 1TSO 8217:2024. Table 9 sets out the characteristics of EMAG in accordance with the specifications described in EN 14214.

[0250] [Tables7] Product VLSFO NOR Specifications ISO8217 Table 2 Reference 411-833 Characteristics Unit Standard Analysis RMG380-0.5 Chemical viscosity @ 5°C mmVs ISO 3104 310.1 < 380.0 > 120.0 Bulk density (single) 15°C ISO 12185 < 991.0 CCAi - - 815 < 870 Sulfur ASTM D2622 4600 < 5000 Flash point Pensky-Martens Ci / -* ISO 2719 107 > 60 Hz mg / lcg iP 570 NM* < 2.00 Acid value mgKQHiîg ASTM 0664 < 0.7 < 2.5 CCR %m ISO 10370 9.25 < 18 Pour point 'C ISO 3016 6 <30 Water %m NF ISO 3733 <0.10 < 0.50 Ash %m ISO 6245 NM' < 0.1 DUE Vanadium mgZkg IP 501 7 < 350 Sodium mg&9 IP 501 13 < 100 Aluminium + Silicon mg / kg IP 501 < 15 <60 Used lubricating oil {Ca and Zn or Ca and P) mg / kg; IP 501 Ca = 15 Zn = 4 HLU present if Ca > 30 and Zn > 15 or Ca > 33 and P > 15 TSF TSA TSE %m ISO103G7-1 ISO10307-2A 1 SOI 0307-26 < 0.01 0.02 = 001 < 0.10 To be indicated To be indicated EMAG content %m as™ D7963 NM* De minimis lève! * MM = our measured

[0251] [Tables8] DMA Product Specifications ISOS217 Table 1 Reference 411-839 Characteristics Unit Standard Analyses DMA Kinematic Viscosity@40°C nnRs ISO3104 2.891 < 6.000 > 2.000 Density@15°C kg / m³ ISO 12185 850.0 < 890.0 Cetane Number ISO 4264 47.8 > 40.0 Sulfur ASTM D2622 540 < 1000 Pensky-Martens Flash Point °C ISO 2719 69 > 60 HsS rng'kg IP 570 < 0.60 < 200 Acid Number mgKOH / g ASTM D664 NM < 0.5 Oxidation Stability g;W ISO 12205 6 < 25 Content EMAG % vol EN 14078 0.18 < de minimis fevel CCR ISO 10370 < 0.10 < 0.30 Cloud point °C ISO 3015 -3 To be specified Maximum boiling point EN 116 -11 To be specified Pour point °C ISO 3015 -13 < -6 Appearance - Colored Clear and limpid* Water mg / kg ISO 3733 70 < 20g Ash ISO 6245 < 9.001 < 0.010 Lubricant pm ISO 12156-1 7 < 520 * If the distillate is colored (as is the case for DMA), then the water content applies

[0252] [Tables9] Product EMAG Specification s EN 14214 Reference 410-584 Characteristics Unit Standard Analyses EMAG Content in EMAG %m EN 14103 >96.5 > 96.5 Density^lS^C kg / m- ISO 12185 883.2 > 860 <900 Density viscosity@40°C francs ISO 3104 4.457 > 3.50 < 5.00 Pensky-Martens 'C' point ISO 2719 > 148 > 101 Cetane number - ISO 5165 51J >51 Copper corrosion rating ISO 2160 IA. Class 1 Foxydadon Stability h EN 14112 11 > 8.0 Acid value mgKCMg EN 14104 <0.5 < 0.50 Iodine value gW100g EN 14111 / &-90 < 120 Methyl ester content of phenylenic acid % ni EN 14163 2.3 < 12.0 Potassium unsaturated methodo ester content %m EN 15779 <1.00 < 100 Methane content %m EN 14110 <O1 < 020 Teneur en mono^rcérides % m EN 14105 <0.35 < 0,70 Teneur en diÿycéndes % m EN 14105 <0.1 < 0.20 Teneur en triglycérides % m EN 14105 <0.1 < 0,20 dycéroi libre % m EN 14105 <0.01 < 0..O2 Glycérol total % m EN 14105 <0.1 < 0.25 Water % m ISO 12937 0 046 < 0.050 Total contamination ^3 EN 12662 < 10 <24 Sulfated ash content % ni ISO 3987 < û 005 < 0.02 Sulphur content <3 < 13.0 Group i metals (Na * K) ^3 EN 14538 <0.5 < 5.0 Group 11 metals (Ca + Mg) mg&g EN 14538 <2 < 5.0 Phosphorus content mg / kg EN 14107 <4 <4.0 Cloud point:°C ISO 3S15 -6.3 According to zone Maximum boiling point:°C EN 116 -13 According to zone Pour point:°C ISO 3016 -12 According to zone.

[0253] The composition characteristics are shown in Table 10. It can be seen that the VLSFO / TPO / EMAG composition meets the specifications of an RF-80 fuel in the standard. The DMA / TPO / EMAG composition meets the specifications of a DFB fuel in the standard, with the exception of the acid number and the Conradson carbon content.

[0254] Table 10 shows the analyses of the mixtures according to tables 1 and 3 of ISO 8217:2024.

[0255] [TableauxlO] Product DFB - ALR1839 RF 80-ALR1888 Components Composition (% mass) TPO EMAG DMA VLSFO 411-728 411-584 411-827 411-833 10 10 20 20 70 70 Characteristics Unit Standard Analysis Spec DFB Analysis Spec RF 80 Nematic viscosity @ 40°G Nematic viscosity @ 50°G mm² / s mnV / s ISO 3104 ISO 3104 3.396 >2 < 11 43.01 ■■ 20 ■ 86 Mass kg^ns ISO 12135 362.6 < 900.0 937.1 < 991.0 Cetane number - ISO 5165 49.9 0P541) > 35 CCAi - - 826 <870 Sulfur %m ASTM D2622 0.15 < 0.50 0.40 < 6 50 Pensky-Martens Flash Point =°C ISO 271S 69.0 > 60.0 92.5 > 60.0 HtS mgrkg IP 570 < 0.60 < 2.00 < 0.60 < 2 00 Acid Number mgKOH / g ASTM D664 0.93 < 0.5 1.00 <2.5 CCR %m ISO 10370 0.42 < 0.30 - 7.33 < 15.00 Pour Point 5°C ISO 3016 -15 <-6 9 <30 Water % vol NF ISO 3733 < 0.65 < 0.30 0.05 < 0.50 Ash %m ISO 6245 <0.001 <0.010 0.63 <0.100 Vanadium mg / kg IP 501 4 <350 Sodium mg / kg IP 501 11 < 100 Aluminium + Silicon mg / kg IP 501 < 15 < 60 Lubricating oil: used mg / kg IP 501 absence TSP ISA TSE %m ISO10307-2A ISO10307-28 ISO10307-1 <0.10 <0.10 <0.10 To be indicated 0.03 <0.10 <0.10 To be indicated ■Oxidation stability h EN 15751 Not suitable >8 EMAG content %m ASTM D7&63 18.9 To be indicated 18.8 To be indicated MTkg ASTM D250 41.475 To be indicated 39.4 To be indicated Additional analyses outside ISO 8217:2024 Oxidation stability msn EN 16091 modified 214.1 - 73.67 - EGN - IP 541 49.9 - 39.4 - Organic chlorine mg / kg EN 14077 < W <50 21 <50 .

[0256] Example 3 - Effect of a performance additive composition

[0257] The effect of a performance additive composition was evaluated on 4 mixtures, a VLSFO consisting solely of fossil-based bases, a VLSFO containing EMAG, a VLSFO containing TPO and a VLSFO containing EMAG and TPO.

[0258] The compositions of the mixtures are found in Table 11. This table shows the influence of the composition of the mixtures and the additive on an ignition parameter (ECN) and a combustion parameter (ABP).

[0259] The tested additive composition, denoted CAdd, comprises a mixture of a cetane number improving additive (an alkyl nitrate), deposition reducing additives (as described in application EP4157971), and phenolic antioxidant additives in relative amounts consistent with those of the previously described additive composition.

[0260] [Tables 11] VLSFO VLSFO / EMA G VLSFO / TPO VLSFO / EMA G / TPO Mixture Composition RSV 62% 62% 62% 62% GO 38% 8% 28% 8% EMAG 30% 20% TPO 10% 10% Cadd 0.4% 0.4% 0.4% 0.4% Ignition and Combustion Parameters ECN 44.2 50.2 41.9 44.9 39.8 41.7 37.3 40.0 ABP (ms) 4.93 3.85 4.82 4.26 4.42 4.19 3.94 4.19

[0261] The ECN ignition parameter (“Estimated Cetane Number”) is measured according to standard IP 541.

[0262] The ABP combustion parameter ("After Burning Period?") is measured according to standard IP541. The ABP parameter corresponds to the duration of combustion which continues in an internal combustion engine after the appearance of the maximum explosion pressure.

[0263] Figures 4 and 5 show the effect of the composition and the additive on the ignition parameter ECN and the combustion parameter ABP.

[0264] In the absence of additives, substituting diesel fuel (GO) with EMAG degrades ignition quality (reduced ECN) and has little impact on combustion quality. Substituting diesel fuel with TPO also degrades ignition quality. However, it improves combustion quality (reducing ABP) just like substituting diesel with an EMAG / TPO blend. The degradation in ignition quality appears to be more pronounced when diesel is replaced by an EMAG / TPO blend compared to compositions where diesel is replaced by EMAG or TPO alone, whereas, conversely, combustion quality is improved.

[0265] The addition of the additive composition greatly improves ignition quality, particularly for the VLSFO mixture, and also improves combustion quality.

[0266] The same effect is observed on all mixtures except for the VLSFO / EMAG / TPO mixture with additives, for which the combustion quality is slightly degraded but remains better than that of the VLSFO / TPO or VLSFO / EMAG mixtures.

Claims

Demands

1. Marine fuel composition comprising: (i) 30 to 90% by mass of a first component comprising at least one 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 0.5% by mass, and a flash point of not less than 60 °C, (ii) 1 to 30% by mass of a second component consisting of tire oil and having a sulfur content of 0 to 1.5% by mass and a flash point of not less than 40 °C, (iii) 5 to 69% by mass of a third component consisting of alkyl esters of fatty acids of renewable origin, in proportions such that said composition has a sulfur content of not more than 0.5% by mass and a flash point of not less than 60 °C.

2. Composition according to claim 1, comprising: (i) 40 to 80% by mass, preferably 45 to 80% by mass, of the first component, (ii) 1 to 20% by mass, preferably 5 to 15% by mass, of the second component, (iii) 5 to 59% by mass, preferably 5 to 50% by mass, of the third component.

3. Composition according to claim 1 or 2 wherein the composition comprises a kinematic viscosity at 50 °C of at least 2 mm2 / s.

4. Composition according to any one of claims 1 to 3, comprising a bio-based carbon content measured according to ASTM D6866-24 of at least 6% by mass, preferably at least 10% by mass, more preferably at least 20% by mass, even more preferably at least 22% by mass, and up to 70% by mass.

5. Composition according to any one of claims 1 to 4 wherein the first component comprises at least one fossil base selected from a distillate, such as an atmospheric distillate or a vacuum distillate, and a hydrocarbon residue, such as an atmospheric residue, a vacuum residue or a visbreaking residue, and Optionally, the first component includes at least one petroleum-based fluxing agent.

6. A composition according to any one of claims 1 to 5 further comprising, from 500 to 5000 ppm by mass, preferably from 1000 to 5000 ppm by mass, a composition of additives comprising: (i) one or more cetane number-enhancing additives selected from alkyl nitrates, aryl peroxides, and alkyl peroxides, (ii) one or more deposition-reducing additives selected from quaternary ammonium salts other than betaines and amido alkyl betaines, wherein the mass ratio of the amount of additive(s) (i) to the amount of additive(s) (ii) is in the range of 4:1 to 1:4, and optionally: (iii) one or more antioxidant additives selected from compounds having at least one alkylphenol group in their structure, in which 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.

7. Composition according to any one of claims 1 to 6 wherein the second component comprises one or more of the following characteristics: - an initial boiling point of 100 °C or more, - a flash point of at least 50 °C, preferably of at least 55 °C, - a sulfur content of 0.8 to 1.5% by mass, preferably of 0.8 to 1.0% by mass, - a bio-based carbon content of 20 to 100% by mass measured according to ASTM D6866-24.

8. Composition according to any one of claims 1 to 7 wherein the third component consists of methyl esters, ethyl esters and / or propyl esters, alone or in mixture.

9. A method for manufacturing a marine fuel composition in which the following are mixed: (i) 30 to 90% by mass of a first component comprising at least one fossil base and having a sulfur content of not more than 1.5% by mass, preferably not more than 1% by mass, more than preferably of not more than 0.5% by mass, and a flash point of at least 60°C, (ii) of 1 to 30% by mass of a second component consisting of tyre oil and having a sulfur content of 0 to 1.5% by mass and a flash point of at least 40°C, and (iii) of 5 to 69% by mass of a third component consisting of alkyl esters of fatty acids of renewable origin, in proportions such that said composition resulting from the mixture has a sulfur content of not more than 0.5% by mass and a flash point of at least 60°C.

10. The process according to claim 9, wherein the following are mixed: (i) 40 to 80% by mass, preferably 45 to 80% by mass, of the first component, (ii) 1 to 20% by mass, preferably 5 to 15% by mass, of the second component, (iii) 5 to 59% by mass, preferably 5 to 50% by mass, of the third component.

11. A method according to claim 9 or 10 wherein the mixture is made in proportions such that the composition further comprises a kinematic viscosity at 50 °C of at least 2 mm2 / s.

12. A process according to any one of claims 9 to 11 wherein the first component comprises at least one fossil base selected from a distillate, such as an atmospheric distillate or a vacuum distillate, and a hydrocarbon residue, such as an atmospheric residue, a vacuum residue or a visbreaking residue, and optionally at least one petroleum-derived fluxant.

13. A process according to any one of claims 9 to 12 wherein the second component comprises one or more of the following characteristics: - an initial boiling point of 100 °C or more, - a flash point of at least 50 °C, preferably of at least 55 °C, - a sulfur content of 0.8 to 1.5% by mass, preferably of 0.8 to 1.0% by mass.

14. A process according to any one of claims 9 to 13 wherein the third component consists of methyl esters, ethyl esters and / or propyl esters, alone or in mixture.

15. A method according to any one of claims 9 to 14, wherein 500 to 5000 ppm by mass are further added to the mixture, preferably from 1000 to 5000 ppm by mass, of an additive composition comprising: (i) one or more cetane number improvers selected from alkyl nitrates, aryl peroxides, and alkyl peroxides, (ii) one or more deposition-reducing additives selected from quaternary ammonium salts other than betaines and amido alkyl betaines, wherein the mass ratio of the amount of additive(s) (i) to the amount of additive(s) (ii) is in the range of 4:1 to 1:4, and optionally: (iii) one or more antioxidant additives selected from compounds having at least one alkylphenol group in their structure, wherein the mass ratio of the amount of additive(s) (i) to the amount of additive(s) (iii) is in the range of 60:1 to 1:

1.

16. Use of a component consisting of alkyl esters of fatty acids from renewable sources to reduce carbon black emissions during the combustion of a mixture containing a first component comprising at least one 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 0.5% by mass, and a flash point of at least 60 °C, and a second component consisting of tire oil having a sulfur content of 0 to 1.5% by mass and a flash point of at least 40 °C, wherein: (i) 30 to 90% by mass of the first component, (ii) 1 to 30% by mass of the second component, and (iii) 5 to 69% by mass of the component consisting of alkyl esters of fatty acids from renewable sources, are mixed in proportions such that the resulting composition of the mixture has a sulfur content of no more than 0.5% by mass and a flash point of at least 60°C.

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