EP4183856A1 - Base for marine fuel comprising a component from a renewable source and method of manufacturing - Google Patents

Abstract

The invention relates to a base for marine fuel comprising a component of renewable origin of the alkyl ester type derived from fatty acids of vegetable or animal origin. The addition of this component of renewable origin makes it possible to improve the viscosity and the stability of a petroleum residue and very particularly of a visbroken residue.

Description

Field of the invention

The present invention relates to a base for marine fuel comprising a component of renewable origin of the methyl ester type derived from fatty acids of plant or animal origin (also designated by the acronym FAME or the acronym FAME in English). The addition of this component of renewable origin makes it possible to improve the viscosity, the pour point and the stability of an oil residue.

Prior art

Marine fuels are usually manufactured by mixing a residue (atmospheric residue, vacuum residue or visbreaking residue) with one or more fluxing agents usually of petroleum origin.

In order to reduce the impact of marine fuels on the environment, producers are seeking to integrate more and more components of renewable origin in their manufacture. In particular, producers seek to manufacture fuels that preferably have a low impact on greenhouse gases such as carbon dioxide, and a low sulfur content because the objective is to reduce sulfur emissions, particularly in arctic regions.

The document WO2020109653A1 describes a marine fuel mixture comprising a marine fuel having a density of 860 to 960 kg/m ³ at 15° C. and from 0.5 to 50% by volume of a renewable hydrotreated fuel. The addition of this renewable fuel improves the pour point and storage stability of the mixture. The renewable hydrotreated fuel used comprises at least 70% vol of C15-C18 paraffins and 0.5% vol or less of oxygenated hydrocarbon compounds. This renewable compound results from the hydrotreatment, and possibly from the isomerization of fatty acids, triglycerides and other derivatives of fatty acids contained in a vegetable or animal oil. This document specifies that it is preferable that the marine combustible mixture does not contain FAME in order to obtain good long-term storage stability. It is indeed known that the oxidation of FAME harms the long-term storage stability of a fuel.

The document WO202118895A1 discloses a fuel mixture having improved stability or compatibility comprising 5 to 95% w/w of a hydrocarbon residue component selected from atmospheric residue and vacuum residue from vacuum distillation of atmospheric residue , from 5 to 50% m/m of a fatty acid methyl ester component and up to 90% m/m of a hydrotreated or non-hydrotreated hydrocarbon component. In order to exhibit the improved stability/compatibility properties, the methyl esters must be added to the hydrocarbon residue component before any other component.

Although such marine fuel mixtures are satisfactory, the search for new marine fuels is still necessary to meet the requirements set by increasingly strict regulations and the needs of consumers.

Summary

The object of the present invention is to provide a low sulfur, improved viscosity, good pour point renewable marine fuel base. Another objective is to provide marine fuel, which can be used in applications where long-term storage stability is required. Yet another object is to provide marine fuel with bio-based content, which can be used with current marine fuel logistics.

Definitions

An atmospheric residue comes from the atmospheric distillation of crude oil (atmospheric distillation column bottom).

A vacuum residue comes from the vacuum distillation of an atmospheric residue (bottom of the vacuum distillation cone).

A residue resulting from a visbreaking process, also called visbreaking residue or visbreaking residue, results from the transformation of a residue under vacuum by visbreaking or “visbreaking”.

• So représente le pouvoir du milieu à solubiliser les asphaltènes (pouvoir solvant), c'est à dire le caractère aromatique du milieu. Plus celui-ci sera aromatique, plus le So sera élevé,
• Sa caractérise la stabilité intrinsèque (ou peptisabilité) des asphaltènes,
• (1-Sa) représente l'aromaticité du milieu nécessaire pour solubiliser les asphaltènes présents.

The characteristic called S value (“S-value”), or even intrinsic stability, is defined in the profession as well as in the ASTM D7157-18 standard (Revision 2018) by the following expression:
S=aromaticity of maltenes/aromaticity of asphaltenes, i.e. S=So/(1-Sa), in which:

• So represents the capacity of the medium to solubilize the asphaltenes (solvent power), that is to say the aromatic character of the medium. The more aromatic it is, the higher the So will be,
• Its characterizes the intrinsic stability (or peptizability) of asphaltenes,
• (1-Sa) represents the aromaticity of the medium necessary to solubilize the asphaltenes present.

If S>1, the asphaltenes are peptized and are therefore stable. S-1 represents the stability reserve (the higher this reserve, the less the product will be subject to precipitation or compatibility problems).

$${\mathit{Sa}}_{\mathit{mélange}}=\frac{{\displaystyle \sum x_i\times {\mathit{ASP}}_i\times {\mathit{Sa}}_i}}{{\displaystyle \sum x_i\times {\mathit{ASP}}_i}}$$

$$S_{\mathit{mélange}}=\frac{{\mathit{So}}_{\mathit{mélange}}}{1-{\mathit{Sa}}_{\mathit{mélange}}}$$

The S-value parameters respond to mixing laws which are written as follows: $${\mathit{So}}_{\mathit{blend}}={\displaystyle \sum x_I\times {\mathit{So}}_I}$$

$${\mathit{Her}}_{\mathit{blend}}=\frac{{\displaystyle \sum x_I\times {\mathit{ASP}}_I\times {\mathit{Her}}_I}}{{\displaystyle \sum x_I\times {\mathit{ASP}}_I}}$$

$$S_{\mathit{blend}}=\frac{{\mathit{So}}_{\mathit{blend}}}{1-{\mathit{Her}}_{\mathit{blend}}}$$

• x_i est la fraction massique du composant i,
• ASP_i est la teneur en asphaltènes (%m) du composant i,
• So_i est le pouvoir solvant du composant i,
• Sa_i est la peptisabilité du composant i.

Or :

• x _i is the mass fraction of component i,
• ASP _i is the asphaltenes content (%m) of component i,
• So _i is the solvent power of component i,
• Its _i is the peptizability of component i.

Note that equation (1) is a simplified form of equation (1bis) below $${\mathit{So}}_{\mathit{blend}}=\frac{{\displaystyle \sum x_I\times \left(100-{\mathit{ASP}}_I\right)\times {\mathit{So}}_I}}{{\displaystyle \sum x_I\times \left(100-{\mathit{ASP}}_I\right)}}$$

For a mixture containing a component for which the So value is not measurable (due for example to the absence of asphaltenes), the So value can be estimated using the method described in document WO 2021/122349 A1 , which is incorporated by reference.

The density at 15° C. is measured according to the ISO 12185:1996 standard.

The viscosity here is the kinematic viscosity, measured at 50° C. or 100° C. or 135° C., for example according to standard ISO 3104:2020.

The pour point is measured according to ISO 3016: 2019.

Sulfur content can be measured according to ISO 8754 or ASTM D4294.

The calculated carbon aromaticity index (CCAI) is calculated according to the Lewis equation (recalled in standard NF ISO 8217-June 2018).

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

detailed description

où VB_mélange est la moyenne pondérée des indices de viscosité du premier composant et du deuxième composant, ces indices de viscosité étant calculés au moyen de la formule: VB_i = 23,097 + 33,469 × Log(Log(v_i + 0,8)) (5),
où v_i est la viscosité cinématique du composant i exprimée en stokes.A first object of the invention relates to the use of alkyl esters of fatty acids to improve the viscosity of a component of at least one hydrocarbon residue, in which is mixed (i) 10 to 70% w/ m of a first component of fatty acid alkyl esters of renewable origin with (ii) 90% to 30% m/m of a second component of at least one hydrocarbon residue, and in which the mixture obtained has a kinematic viscosity lower than a kinematic viscosity calculated according to the formula: $$\vartheta =\exp \left(\exp \left(\frac{{\mathit{VB}}_{\mathit{blend}}-\mathrm{23,097}}{\mathrm{33,469}}\right)\right)-0.8$$

where VB _mixture is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated by means of the formula: VB _i = 23.097 + 33.469 × Log ( Log ( v _i + 0.8)) (5),
where v _i is the kinematic viscosity of component i expressed in stokes.

These different formulas (4) (5) correspond to the so-called Refutas method ( Maples, RE, 2000, "Petroleum Refinery Process Economics", PennWell, ISBN 978-0-87814-779-3 )

In one embodiment, the mixture obtained may have a measured S-value greater than a calculated S-value S _mixture , previously defined with reference to equations (1) to (3). The solvent power of the first component is estimated from a correlation expressing the solvent power So of said first component as a function of the kinematic viscosity at 50°C, the kinematic viscosity at 100°C and the density at 15°C of said first making up. This correlation can be established by following the teaching of the document WO 2021/122349 A1 .

The fatty acid alkyl esters can thus be used to make a marine fuel base with improved viscosity. In other words, these fatty acid alkyl esters can be used to make a mixture which can form a marine fuel base or a marine fuel.

1. (i) 10 à 70 % m/m d'un premier composant d'esters alkyliques d'acides gras d'origine renouvelable,
2. (ii) 90 à 30% m/m d'un deuxième composant d'au moins un résidu d'hydrocarbures, ladite base présentant une viscosité cinématique inférieure à une viscosité cinématique calculée selon la formule : $$\vartheta =\exp \left(\exp \left(\frac{{\mathit{VB}}_{\mathit{mélange}}-\mathrm{23,097}}{\mathrm{33,469}}\right)\right)-\mathrm{0,8}$$
   

où VB_mélange est la moyenne pondérée des indices de viscosité du premier composant et du deuxième composant, ces indices de viscosité étant calculés au moyen de la formule de Réfutas : VB_i = 23,097 + 33,469 × Log(Log(v_i + 0,8)) (5) où v_i est la viscosité cinématique du composant i exprimée en stokes.Thus, another object of the invention relates to a base for marine fuel comprising:

1. (i) 10 to 70% m/m of a first component of alkyl esters of fatty acids of renewable origin,
2. (ii) 90 to 30% m/m of a second component of at least one hydrocarbon residue, said base having a kinematic viscosity lower than a kinematic viscosity calculated according to the formula: $$\vartheta =\exp \left(\exp \left(\frac{{\mathit{VB}}_{\mathit{blend}}-\mathrm{23,097}}{\mathrm{33,469}}\right)\right)-0.8$$
   

where VB _mixture is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated using the Refutas formula: VB _i = 23.097 + 33.469 × Log(Log(v _i + 0.8 )) (5) where v _i is the kinematic viscosity of component i expressed in stokes.

The use of the fatty acid alkyl ester component can thus make it possible to obtain a mixture having a kinematic viscosity at 50° C. that is 15 to 75% lower than the calculated viscosity. This lowering of kinematic viscosity is particularly important when the fatty acid alkyl ester component is added to a visbreaking residue or a mixture of visbreaking residues, with a 20 to 70% drop in viscosity compared to the calculated viscosity whereas it is 15 to 40% for the other residues (with equal content of alkyl ester component).

The use of the component of fatty acid alkyl esters can also make it possible to obtain a mixture having a kinematic viscosity at 100° C. of 5 to 30% lower than the calculated viscosity. This lowering of kinematic viscosity is also greater when the fatty acid alkyl ester component is added to a visbreaking residue or a mixture of visbreaking residues, with a 10 to 30% drop in viscosity compared to at the calculated viscosity whereas it is 5 to 20% for the other residues (with equal content of alkyl ester component).

Thus, surprisingly, the fatty acid alkyl ester component acts as a fluxing agent for the second component, producing an effect on the viscosity which is greater than the expected effect. The first component can therefore advantageously be used as a flux for the preparation of a base for marine fuel. In particular, the reduction in viscosity obtained by adding the first component is a definite advantage, since the temperatures of use can be significantly reduced.

Additionally, when the second component is at least one hydrocarbon residue selected from a vacuum residue and a visbreaking residue, fatty acid alkyl esters have surprisingly been observed to have an effect on the pour point mixture (typically determined according to the ISO 3016-2019 standard) greater than the effect provided by fluxes of petroleum origin usually used. In particular, the difference between the pour point of the first component of fatty acid alkyl esters and the pour point of the mixture increases with the content of the first component of the mixture, this difference in absolute value being greater than the difference in absolute value between the pour point of a flux of petroleum origin and the pour point of a mixture of this flux of petroleum origin with the second component (in other words, for a mixture in which the first component has been replaced by a fluxing agent of petroleum origin). This effect is greater for visbreaking residues than for vacuum residues.

Advantageously, when the second component is at least one hydrocarbon residue chosen from a vacuum residue and a visbreaking residue, the base for marine fuel can have a measured S-value greater than a calculated S-value S _mixture as previously defined, using a value of the solvent power of the first component estimated from a correlation expressing the solvent power So of said first component as a function of the kinematic viscosity at 50°C, the kinematic viscosity at 100°C and the density at 15°C of said first component.

Finally, the subject of the invention is a marine fuel comprising the base for marine fuel according to the invention and optionally at least one fluxing agent of petroleum origin.

Due to the effect on the viscosity of the component of alkyl esters, the base according to the invention makes it possible to manufacture a marine fuel requiring a reduced quantity, or even zero, of fluxing agent of petroleum origin.

où VB_mélange est la moyenne pondérée des indices de viscosité du premier composant et du deuxième composant, ces indices de viscosité étant calculés au moyen de la formule de Réfutas : $${\mathit{VB}}_i=\mathrm{23,097}+\mathrm{33,469}\times \mathit{Log}\left(\mathit{Log}\left(v_i+\mathrm{0,8}\right)\right)$$

où v_i est la viscosité cinématique du composant i exprimée en stokes.The invention also relates to a process for improving the viscosity of a component of at least one hydrocarbon residue comprising the mixture of (i) 10 to 70% m/m of a first component of esters alkyl fatty acids of renewable origin with (ii) 90% to 30% m/m of a second component of at least one hydrocarbon residue, and in which the mixture obtained has a viscosity lower than a calculated viscosity according to the formula: $$\vartheta =\exp \left(\exp \left(\frac{{\mathit{VB}}_{\mathit{blend}}-\mathrm{23,097}}{\mathrm{33,469}}\right)\right)-0.8$$

where VB _mixture is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated using the Refutas formula: $${\mathit{VB}}_I=\mathrm{23,097}+\mathrm{33,469}\times \mathit{Log}\left(\mathit{Log}\left(v_I+0.8\right)\right)$$

where v _i is the kinematic viscosity of component i expressed in stokes.

First component of alkyl esters

Fatty acid alkyl esters 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 trans-esterification. Alternatively, fatty acid alkyl esters can be produced by reacting a fatty acid with an alcohol (esterification reaction) to form a fatty acid ester.

The first component is therefore exclusively of biological origin: we will speak of a component of renewable origin.

The vegetable oils can be chosen from pine oil, rapeseed oil, sunflower oil, castor oil, peanut oil, linseed oil, babasu oil, hemp oil, linola oil, jatropha oil, peanut oil, rice bran oil, mustard oil, carinata oil, walnut oil coconut oil, coconut oil, olive oil, palm oil, cottonseed oil, corn oil, palm kernel oil, soybean oil, pumpkin oil , grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, chinawood oil, rice oil, safflower oil, algae oil, waste oils, and any combination thereof.

Waste oils include used cooking oils (used food oils) and oils recovered from waste water, such as trap and drain grease/oils, gutter oils, sewage oils, e.g. water treatment plants, and used fats from the food industry.

Animal fats can be selected from tallow, lard, shortening (yellow and brown fat), fish oils/fats, milk fat and any combination thereof.

The alcohol 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.

In a preferred embodiment, the alkyl esters component comprises, or consists of, methyl esters, ethyl esters, propyl esters, alone or in admixture, preferably methyl esters, ethyl esters, alone or in admixture , for example methyl esters.

Second component of at least one hydrocarbon residue

The at least one hydrocarbon residue of the second component can be chosen from a residue resulting from a distillation process or a residue resulting from a visbreaking process.

The residue from the distillation process can be an atmospheric residue or a vacuum residue.

In one embodiment, the second component is at least one hydrocarbon residue selected from vacuum residue and visbreaking residue.

In a preferred embodiment, the at least one hydrocarbon residue of the second component is a visbreaking residue.

The second component is therefore exclusively of petroleum origin.

Advantageously, the second component may consist of at least one hydrocarbon residue, in particular as previously described.

Advantageously, the at least one hydrocarbon residue of the second component may have a sulfur content of at most 1.5% m/m, preferably of at most 1% m/m, or even of at most 0 .8% m/m.

• pour une teneur en soufre d'au plus 1,5%m/m, de préférence d'au plus 1% m/m :
  • ∘ une teneur en asphaltènes inférieure à 3%m/m,
  • ∘ un résidu de carbone inférieur à 15% m/m,
• quelle que soit la teneur en soufre, une valeur Sa supérieure à 0,75.

When the residue is a vacuum residue, it may have at least one of the following characteristics:

• for a sulfur content of at most 1.5% m/m, preferably of at most 1% m/m:
  • ∘ an asphaltene content of less than 3%m/m,
  • ∘ a carbon residue of less than 15% m/m,
• regardless of the sulfur content, a Sa value greater than 0.75.

• pour une teneur en soufre d'au plus 1,5%m/m, de préférence d'au plus 1% m/m :
  • ∘ une teneur en asphaltènes supérieure à 3%m/m,
  • ∘ un résidu de carbone supérieur à 15% m/m,
• quelle que soit la teneur en soufre, une valeur Sa inférieure à 0,70.

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

• for a sulfur content of at most 1.5% m/m, preferably of at most 1% m/m:
  • ∘ an asphaltene content greater than 3%m/m,
  • ∘ a carbon residue greater than 15% m/m,
• regardless of the sulfur content, a Sa value of less than 0.70.

Marine fuel base

The base for marine fuel according to the invention contains from 10 to 70% m/m of the first component of fatty acid alkyl esters and from 90 to 30% m/m of the second component of at least one hydrocarbon residue . These contents are given relative to the total composition of the base. Typically, the sum of the contents of first component and second component is equal to 100%. In other words, the base can consist only of the first and second components.

In one embodiment, the base may contain the first component in a content of 10 to 60% m/m, 10 to 50% m/m, 10 to 50% m/m or in any range defined by two of these limits, the rest of the base being made up of the second component.

The content of the first component of the base according to the invention, and in particular of methyl esters, can be determined by the test methods IP579 or ASTM D7963, as described in the ISO 8217-2018 standard.

The base according to the invention can be obtained by simple mixing of the first and second components described above.

In order to facilitate their mixing, the two components, or at least the second component, can be preheated, for example to a temperature lowering the viscosity of the second component. A person skilled in the art will be able to determine an appropriate preheating temperature.

• une masse volumique de 860 à 991 kg/m³ à 15°C,
• une teneur en soufre inférieure ou égale à 0,7% en masse,
• un point d'écoulement d'au plus 42°C,
• un CCAI d'au plus 870,
• une viscosité cinématique à 50°C d'au plus 2000mm²/s.

The marine fuel base may have one or more of the following characteristics:

• a density of 860 to 991 kg/m ³ at 15°C,
• a sulfur content less than or equal to 0.7% by mass,
• a pour point of not more than 42°C,
• a CCAI of no more than 870,
• a kinematic viscosity at 50° C. of at most 2000 mm ² /s.

• une masse volumique à 15°C de 900 à 980 kg/m³ ou de 920 à 960 kg/m³, ou dans tout intervalle défini par deux de ces limites,
• une teneur en soufre inférieure ou égale à 0,7% en masse,
• un point d'écoulement d'au plus 42°C, typiquement de 25 à 42°C,
• un CCAI d'au plus 870,
• une viscosité cinématique à 50°C d'au plus 80mm²/s, typiquement de 25 à 80 mm²/s.

When the second component of the base for marine fuel comprises only, or even consists of, one or more atmospheric residues, the base may have one or more of the following characteristics:

• a density at 15°C of 900 to 980 kg/m ³ or of 920 to 960 kg/m ³ , or in any interval defined by two of these limits,
• a sulfur content less than or equal to 0.7% by mass,
• a pour point of at most 42°C, typically 25 to 42°C,
• a CCAI of no more than 870,
• a kinematic viscosity at 50° C. of at most 80 mm ² /s, typically from 25 to 80 mm ² /s.

• une masse volumique à 15°C de 930 à 980 kg/m³ ou de 940 à 970 kg/m³, ou dans tout intervalle défini par deux de ces limites,
• une teneur en soufre inférieure ou égale à 0,7% en masse,
• un point d'écoulement d'au plus 12°C ou d'au plus 0°C, par exemple de -6° à -30°C,
• un CCAI d'au plus 860,
• une viscosité cinématique à 50°C d'au plus 380 mm²/s, par exemple de 50 à 380 mm²/s,
• une S-value supérieure à 3, typiquement de 3 à 7.

When the second component of the base for marine fuel comprises only, or even consists of, one or more vacuum residues, the base may have one or more of the following characteristics:

• a density at 15°C of 930 to 980 kg/m ³ or of 940 to 970 kg/m ³ , or in any interval defined by two of these limits,
• a sulfur content less than or equal to 0.7% by mass,
• a pour point of at most 12°C or at most 0°C, for example from -6° to -30°C,
• a CCAI of no more than 860,
• a kinematic viscosity at 50° C. of at most 380 mm ² /s, for example from 50 to 380 mm ² /s,
• an S-value greater than 3, typically 3 to 7.

• une masse volumique à 15°C de 910 à 991 kg/m³,
• une teneur en soufre inférieure ou égale à 0,7% en masse,
• un point d'écoulement d'au plus 12°C, par exemple de 12° à -42°C, ou de 6° à -36°C, ou dans tout intervalle défini par deux de ces limites,
• un CCAI d'au plus 870 ou d'au plus 840, par exemple de 820 à 870,
• une viscosité cinématique à 50°C d'au plus 2000 mm²/s, par exemple de 25 à 2000 mm²/s,
• une S-value supérieure à 1,5, par exemple de 1,5 à 4 ou de 1,5 à 3, ou dans tout intervalle défini par deux de ces limites.

When the second component of the base for marine fuel comprises only, or even consists of, one or more visbreaking residues, the base may have one or more of the following characteristics:

• a density at 15°C of 910 to 991 kg/m ³ ,
• a sulfur content less than or equal to 0.7% by mass,
• a pour point of at most 12°C, for example from 12° to -42°C, or from 6° to -36°C, or in any interval defined by two of these limits,
• a CCAI of at most 870 or at most 840, for example from 820 to 870,
• a kinematic viscosity at 50° C. of at most 2000 mm ² /s, for example from 25 to 2000 mm ² /s,
• an S-value greater than 1.5, for example from 1.5 to 4 or from 1.5 to 3, or in any interval defined by two of these limits.

marine fuel

The base according to the invention can be used as a base for manufacturing marine fuel. By marine fuel, we mean a fuel with specifications suitable for use in diesel engines and boilers of ships, before any conventional treatment on board (decantation, centrifugation, filtration) prior to their use. This type of fuel can also be used in stationary diesel engines, of the same or similar type as those used for marine applications.

For this purpose, the base according to the invention is typically mixed with a flux of petroleum origin. However, it can also be used alone as marine fuel. The marine fuel according to the invention can in particular comply with all the specifications of marine fuels presented in the ISO 8217-June 2018 standard, except for the content of FAME or other methyl esters.

The marine fuel can in particular comply with the specifications of the RMD, RME, RMG, RMK type fuels of the standard (except for the content of methyl esters).

• les gazoles issus de la distillation directe du pétrole : kérosène, pétrole lampant, gazole léger, gazole moyen, gazole lourd,
• les produits de distillation sous vide du résidu atmosphérique : gazole léger sous vide, gazole moyen sous vide, gazole lourd sous vide, distillat,
• les produits de distillation atmosphérique ou sous vide des effluents des unités de conversion : gazole de viscoréduction, distillat de viscoréduction,
• les produits issus des unités de craquage catalytiques et des unités de désulfuration et hydrodésulfuration : gazole de craqueur catalytique (LCO), gazoles lourds de craqueur catalytique (HCO, huile claire, Slurry), gazole désulfuré, gazole et bleed (résidu) des unités d'hydrodésulfuration,
• les produits issus des unités de vapocraquage : huile ou essence de pyrolyse.

This flux of petroleum origin is for example chosen from:

• diesel from the direct distillation of petroleum: kerosene, kerosene, light diesel, medium diesel, heavy diesel,
• vacuum distillation products of the atmospheric residue: light vacuum gas oil, medium vacuum gas oil, heavy vacuum gas oil, distillate,
• products of atmospheric or vacuum distillation of effluent from conversion units: visbreaking gas oil, visbreaking distillate,
• products from catalytic cracking units and desulphurization and hydrodesulphurization units: diesel from catalytic cracker (LCO), heavy diesel from catalytic cracker (HCO, light oil, Slurry), desulphurized diesel, diesel and bleed (residue) from units of hydrodesulfurization,
• products from steam cracking units: pyrolysis oil or gasoline.

The characteristics of the marine fuel such as its viscosity, its density and its sulfur content can be adjusted by varying the proportions of flux of petroleum origin and of base for marine fuel according to the invention.

Typically, the content of fluxing agent of petroleum origin in the marine fuel can be from 0 to 30% m/m, preferably from 0 to 20% m/m, the remainder being constituted by the base for marine fuel according to the invention.

In one embodiment, the marine fuel according to the invention may have a first component content of fatty acid alkyl esters of 7 to 38% m/m, a second component content of at least one residue of 42 at 85.5% m/m and a flux content of petroleum origin of 0 to 30% m/m.

In another embodiment, the marine fuel according to the invention may have a first component content of fatty acid alkyl esters of 8 to 38% m/m, a second component content of at least one residue of 48 to 72% m/m and a flux content of petroleum origin of 0 to 20% m/m.

• une teneur en soufre inférieure ou égale à 1,5% m/m, de préférence inférieure ou égale à 1%m/m, davantage de préférence inférieure ou égale à 0,5% m/m, par exemple de 0,05 à 0,5% m/m ou dans tout intervalle défini par deux de ces limites,
• une masse volumique à 15°C d'au plus 1010 kg/m³, d'au plus 991 kg/m³, d'au plus 975 kg/m³, d'au plus 960 kg/m³, d'au plus 920 kg/m³, d'au plus 900 kg/m³ ou d'au plus 890 kg/m³, notamment supérieure à 900 kg/m³, ou dans tout intervalle défini par deux de ces limites,
• un point d'écoulement d'au plus 30°C, d'au plus 6°C, d'au plus 0°C ou d'au plus -6°C, notamment supérieure à -42 °C, ou dans tout intervalle défini par deux de ces limites
• une viscosité cinématique à 50°C d'au plus 700 mm²/s, d'au plus 500 mm²/s, d'au plus 380 mm²/s, d'au plus 180 mm²/s, d'au plus 80 mm²/s, d'au plus 30 mm²/s ou d'au plus 10 mm²/s, notamment supérieure à 2mm²/s, ou dans tout intervalle défini par deux de ces limites.

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

• a sulfur content less than or equal to 1.5% m/m, preferably less than or equal to 1% m/m, more preferably less than or equal to 0.5% m/m, for example from 0.05 to 0.5% m/m or within any interval defined by two of these limits,
• a density at 15°C of not more than 1010 kg/m ³ , not more than 991 kg/m ³ , not more than 975 kg/m ³ , not more than 960 kg/m ³ , not more than more than 920 kg/m ³ , not more than 900 kg/m ³ or not more than 890 kg/m ³ , in particular greater than 900 kg/m ³ , or in any interval defined by two of these limits,
• a pour point of not more than 30°C, not more than 6°C, not more than 0°C or not more than -6°C, in particular greater than -42°C, or in any interval defined by two such limits
• a kinematic viscosity at 50°C of not more than 700 mm ² /s, not more than 500 mm ² /s, not more than 380 mm ² /s, not more than 180 mm ² /s, not more than more than 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, or in any interval defined by two of these limits.

The invention makes it possible in particular to formulate a marine fuel with a very low sulfur content (less than 0.50% sulfur), comprising a renewable component.

Examples:

Different bases for marine fuel have been prepared, each comprising a residue (atmospheric residue, vacuum residue or visbreaking residue depending on the tests) and a fluxing agent of petroleum origin or of biological origin.

The residues used are visbreaking residues (denoted RVR), a vacuum residue (denoted RSV) and an atmospheric residue (denoted RAT). The fluxes of renewable origin tested are fatty acid methyl esters from the transesterification of vegetable oils (denoted FAME 0, FAME 1 and FAME 2) and fatty acid methyl esters from the transesterification of vegetable oils. cooking (noted UCOME). The petroleum-based fluxing agent is a diesel (denoted GO).

The characteristics of the various components used for the bases are collated in Tables 1 (residues) and 2 (fluxants).

où :

• A, B, C, D : coefficients déterminés par traitement statistique tel que décrit dans WO 2021/122349 A1 ,
• v ₅₀ : Viscosité cinématique (en mm²/s) à 50°C,
• v ₁₀₀ : Viscosité cinématique (en mm²/s) à 100°C,
• CCAI: "Calculated Carbon Aromaticity Index" (indice calculé d'aromaticité du carbone), défini par : $$\mathit{CCAI}={\rho }_{15}-81-141.\mathit{Log}\left[\mathit{Log}\left({\nu }_{50}+\mathrm{0,85}\right)\right]-483.\mathit{Log}\frac{T+273}{323}$$
  
• où
• ρ ₁₅ : masse volumique à 15°C (en kg/m³), T : température (en °C).

Tableau 1 : Caractéristiques des résidus Produit RVR 1 (411-392) RVR 2 (411-445) RSV (411-669) RAT 411-338) Caractéristique Unité Norme Analyse Viscosité à 50°C mm²/s ISO 3104 :2020 4435 8900 2848 219,5 Viscosité à 100°C mm²/s ISO 3104 :2020 139,9 227,6 118 21,36 Viscosité à 135°C mm²/s ISO 3104 :2020 35,81 50,64 Masse volumique à 15°C kg/m³ ISO 12185 :1996 995,4 998,2 984,4 951,0 CCAI - - 835 833 827 818 Soufre %m ASTM D2622 : 16 1,094 0,698 0,711 0,683 Point d'écoulement °C ISO 3016 :2019 36 Asphaltènes %m NF T 60-115 (janvier 2020) 8,33 7,35 2,29 CCR %m ISO 10370 :2014 18,37 19,52 12,58 S-Value S 1,66 2,06 6,42 Sa ASTM D7157-18 0,56 0,62 0,88 So 0,73 0,78 0,77 Tableau 2 : Caractéristiques des fluxants Produit GO 411-393 EMAG 0 410-321 EMAG 1 410-308 EMAG 2 410-182 UCOME 410-241 Caractéristique Unité Analyse Viscosité à 50°C mm²/s 3,274 3,665 3,424 3,667 3,819 Viscosité à 100°C mm²/s 1,482 1,744 1,667 1,743 1,794 Masse volumique à 15°C kg/m³ 857,5 882,0 885,5 882,7 884,9 CCAI - 806 827 828 Soufre %m 0,00455 0 Point d'écoulement °C 0 -12 0 -6 3 Asphaltènes %m 0 0 0 0 0 S-Value So 0,31 0,38 0,38 Tableau 3 : Base comprenant un résidu viscoréduit Produit (point d'écoulement) Composition massique des mélanges RVR 1 (non mesurable) 411-392 80 80 EMAG 0 (-12°C) 410-321 20 - GO (0°C) 411-393 - 20 Caractéristique Unité Norme Analyse Viscosité à 50°C mesurée mm²/s ISO 3104-2020 234,9 329,2 V50 calculée 399,5 372,8 écart en % vs mesure -70 -13 Reproductibilité (%) 7,4 7,4 Viscosité à 100°C mesurée mm²/s ISO 3104-2020 28,15 31,61 V100 calculée 35,7 32,6 écart en % vs mesure -27 -3 Reproductibilité (%) 5 5 Masse volumique à 15°C kg/m³ ISO 12185 : 1996 970,2 965,0 CCAI - - 836 827 Point d'écoulement °C ISO 3016 :2019 -18 S-value mesurée S ASTM D7157-18 1,77 Sa 0,55 So 0,79 S-value calculée S 1,50 1,46 Sa 0,56 0,56 So 0,66 0,64 Tableau 4 : Bases RVR + fluxant pétrolier Produit (point d'écoulement) Composition massique des mélanges RVR 2 (non mesurable) 441-445 90 80 70 60 45 GO (0°C) 411-393 10 20 30 40 55 Caractéristique Unité Analyse Viscosité à 50°C mesurée mm²/s 1743 480,8 164,5 67,54 24,46 V50 calculée 1889 521,9 179,1 73,49 25,13 écart en % vs mesure -8 -9 -9 -9 -3 Reproductibilité (%) 7,4 7,4 7,4 7,4 7,4 Viscosité à 100°C mesurée mm²/s 85,51 40,76 21,14 12,1 6,133 V100 calculée 89,06 40,70 21,09 12,08 6,07 écart en % vs mesure -4 0 0 0 1 Reproductibilité (%) 4 5 6 7 9 Masse volumique à 15°C mesurée kg/m³ 981,0 966,1 950,9 936,6 916 CCAI - 828 825 821 818 814 Point d'écoulement °C 3 -9 -12 -15 -15 Ecart au point d'écoulement du fluxant 3 -9 -12 -15 -15 S-value mesurée S 1,89 1,86 1,75 1,67 1,52 Sa 0,62 0,61 0,62 0,61 0,62 So 0,72 0,73 0,67 0,64 0,58 S-value calculée S 1,92 1,79 1,66 1,54 1,35 Sa 0,62 0,62 0,62 0,62 0,62 So 0,73 0,68 0,63 0,58 0,51 Ecart entre S-value mesurée et calculée -0,03 0,07 0,09 0,13 0,17 Reproductibilité de la méthode sur la S-value mesurée 0,31 0,31 0,30 0,29 0,27 Tableau 5 : Bases RVR + fluxant renouvelable Produit (point d'écoulement) Composition massique des mélanges RVR 2 (non mesurable) 90 80 70 60 35 EMAG 0 (-12°C) 10 20 30 40 65 Caractéristique Unité Analyse Viscosité à 50°C mesurée mm²/s 1361 347,5 124,2 54,43 13,08 V50 calculée 1982 565,2 198,0 82,15 15,90 écart en % vs mesure -46 -63 -59 -51 -22 Reproductibilité (%) 7,4 7,4 7,4 7,4 7,4 Viscosité à 100°C mesurée mm²/s 80,13 36,61 19,52 11,62 4,391 V100 calculée 94,24 44,76 23,79 13,87 4,84 écart en % vs mesure -18 -22 -22 -19 -10 Reproductibilité (%) 4 5 6 7 11 Masse volumique à 15°C mesurée kg/m³ 984,4 971,6 959,5 947,5 919,6 CCAI - 833 833 833 832 830 Point d'écoulement °C 0 -18 -30 -33 -30 S-value mesurée S 2,05 2,28 2,26 2,36 2,42 Sa 0,62 0,61 0,61 0,61 0,62 So 0,77 0,89 0,89 0,93 0,93 S-value calculée S 1,94 1,83 1,72 1,61 1,35 Sa 0,62 0,62 0,62 0,62 0,62 So 0,74 0,69 0,65 0,61 0,50 Ecart entre S-value mesurée et calculée 0,11 0,45 0,54 0,75 1,07 Reproductibilité de la méthode sur la S-value mesurée 0,33 0,35 0,35 0,36 0,36 Tableau 6 : Bases contenant du RSV Produit (point d'écoulement) Composition massique des mélanges RSV (non mesurable) 411-469 80,0 80,0 70,0 70,0 70,0 EMAG 0 (-12°C) 410-321 20,0 0,0 30,0 0,0 0,0 GO (0°C) 411-393 0,0 20,0 0,0 30,0 0,0 UCOME (3°C) 411-241 30,0 Caractéristique Unité Analyse Viscosité à 50°C (mesurée) mm²/s 223,4 269,5 95,11 113,3 98,69 V50 calculée 297 276 123 112,3 127,1 écart en % vs mesure -33 -2 -29 1 -29 Reproductibilité (%) 7,4 7,4 7,4 7,4 7,4 Viscosité à 100°C (mesurée) mm²/s 28,29 30,28 16,69 17,37 16,96 V100 calculée 30,6 28,1 17,9 16 18,2 écart en % vs mesure -8 7 -7 8 -7 Reproductibilité (%) 5 5 6 6 6 Masse volumique à 15°C kg/m³ 961,9 956,6 951,4 943,1 952,1 CCAI - 829 821 829 818 829 Point d'écoulement °C -24 -3 -24 -9 -9 S-value mesurée S 5,84 4,88 5,50 4,88 6,01 Sa 0,87 0,86 0,88 0,85 0,85 So 0,75 0,67 0,67 0,72 0,89 S-value calculée S 5,75 5,64 5,50 5,25 5,43 Sa 0,88 0,88 0,88 0,88 0,88 So 0,69 0,68 0,65 0,63 0,65 Ecart entre S-value mesurée et calculée 0,09 -0,76 0,08 -0,37 0,58 Reproductibilité de la méthode sur la S-value mesurée 0,70 0,61 0,67 0,61 0,72 Tableau 7 : Bases contenant du RAT Produit (point d'écoulement) Composition massique des mélanges RAT (36°C) 411-338 80,0 80,0 70,0 70,0 70,0 70,0 EMAG 0 (-12°C) 410-321 20,0 0,0 30,0 0,0 EMAG 1 (0°C) 410-308 30,0 EMAG 2 (-6°C) 410-182 30,0 GO (0°C) 411-393 0,0 20,0 0,0 30,0 Caractéristique Unité Analyse Viscosité à 50°C (mesurée) mm²/s 50,09 57,1 29,44 33,34 28,17 29,55 V50 calculée 64,3 60,9 38,6 35,9 36,93 38,54 écart en % vs mesure -28 -7 -31 -8 -31 -30 Viscosité à 100°C (mesurée) mm²/s 9,535 9,814 6,937 7,066 6,759 6,925 V100 calculée 10,6 10 7,9 7,2 7,703 7,7886 écart en % vs mesure -11 -2 -14 -2 -14 -12 Masse volumique à 15°C kg/m³ 936,6 931,3 929,4 921,6 930,2 929,3 CCAI - Point d'écoulement °C 36 33 33 30 33 33 Point d'écoulement calculé 33 33 31 31 32 31 All the analyzes presented in tables 2 to 8 were carried out according to the standards appearing in tables 1 and 3. It should be noted that the S ₀ values of the fluxes in table 2 were estimated from a correlation established according to the method described in the document WO 2021/122349 A1 . The correlation used for the different fluxes is the same and is of the form: $$\mathit{So}=\mathrm{AT}+B.{\nu }_{50}+\mathrm{VS}.{\nu }_{100}+D.\mathit{CCIC}$$

Or :

• A, B, C, D : coefficients determined by statistical processing as described in WO 2021/122349 A1 ,
• v ₅₀ : Kinematic viscosity (in mm ² /s) at 50°C,
• v ₁₀₀ : Kinematic viscosity (in mm ² /s) at 100°C,
• CCAI : "Calculated Carbon Aromaticity Index", defined by: $$\mathit{CCIC}={\rho }_{15}-81-141.\mathit{Log}\left[\mathit{Log}\left({\nu }_{50}+0.85\right)\right]-483.\mathit{Log}\frac{T+273}{323}$$
  
• Or
• ρ ₁₅ : density at 15°C (in kg/m ³ ), T : temperature (in °C).

Table 1: Residual characteristics Product RVR 1 (411-392) RVR 2 (411-445) RSV (411-669) RAT 411-338) Characteristic Unit Standard Analysis Viscosity at 50°C mm ² /s ISO 3104:2020 4435 8900 2848 219.5 Viscosity at 100°C mm ² /s ISO 3104:2020 139.9 227.6 118 21.36 Viscosity at 135°C mm ² /s ISO 3104:2020 35.81 50.64 Density at 15°C kg/ ^m3 ISO 12185:1996 995.4 998.2 984.4 951.0 CCIC - - 835 833 827 818 Sulfur %m ASTM D2622: 16 1,094 0.698 0.711 0.683 Pour point °C ISO 3016:2019 36 asphaltenes %m NF T 60-115 (January 2020) 8.33 7.35 2.29 CCR %m ISO 10370:2014 18.37 19.52 12.58 S-Value S 1.66 2.06 6.42 Her ASTM D7157-18 0.56 0.62 0.88 So 0.73 0.78 0.77 Product GO 411-393 FAME 0 410-321 FAME 1 410-308 FAME 2 410-182 UCOME 410-241 Characteristic Unit Analysis Viscosity at 50°C mm ² /s 3,274 3,665 3,424 3,667 3,819 Viscosity at 100°C mm ² /s 1,482 1,744 1,667 1,743 1,794 Density at 15°C kg/ ^m3 857.5 882.0 885.5 882.7 884.9 CCIC - 806 827 828 Sulfur %m 0.00455 0 Pour point °C 0 -12 0 -6 3 asphaltenes %m 0 0 0 0 0 S-Value So 0.31 0.38 0.38 Product (pour point) Mass composition of mixtures RVR 1 (not measurable) 411-392 80 80 FAME 0 (-12°C) 410-321 20 - GO (0°C) 411-393 - 20 Characteristic Unit Standard Analysis Viscosity at 50°C measured mm ² /s ISO 3104-2020 234.9 329.2 V50 calculated 399.5 372.8 deviation in % vs measurement -70 -13 Reproducibility (%) 7.4 7.4 Viscosity at 100°C measured mm ² /s ISO 3104-2020 28.15 31.61 V100 calculated 35.7 32.6 deviation in % vs measurement -27 -3 Reproducibility (%) 5 5 Density at 15°C kg/ ^m3 ISO 12185: 1996 970.2 965.0 CCIC - - 836 827 Pour point °C ISO 3016:2019 -18 S-value measured S ASTM D7157-18 1.77 Her 0.55 So 0.79 Calculated S-value S 1.50 1.46 Her 0.56 0.56 So 0.66 0.64 Product (pour point) Mass composition of mixtures RVR 2 (not measurable) 441-445 90 80 70 60 45 GO (0°C) 411-393 10 20 30 40 55 Characteristic Unit Analysis Viscosity at 50°C measured mm ² /s 1743 480.8 164.5 67.54 24.46 V50 calculated 1889 521.9 179.1 73.49 25.13 deviation in % vs measurement -8 -9 -9 -9 -3 Reproducibility (%) 7.4 7.4 7.4 7.4 7.4 Viscosity at 100°C measured mm ² /s 85.51 40.76 21.14 12.1 6,133 V100 calculated 89.06 40.70 21.09 12.08 6.07 deviation in % vs measurement -4 0 0 0 1 Reproducibility (%) 4 5 6 7 9 Density at 15°C measured kg/ ^m3 981.0 966.1 950.9 936.6 916 CCIC - 828 825 821 818 814 Pour point °C 3 -9 -12 -15 -15 Flow point deviation of the flux 3 -9 -12 -15 -15 S-value measured S 1.89 1.86 1.75 1.67 1.52 Her 0.62 0.61 0.62 0.61 0.62 So 0.72 0.73 0.67 0.64 0.58 Calculated S-value S 1.92 1.79 1.66 1.54 1.35 Her 0.62 0.62 0.62 0.62 0.62 So 0.73 0.68 0.63 0.58 0.51 Difference between measured and calculated S-value -0.03 0.07 0.09 0.13 0.17 Reproducibility of the method on the measured S-value 0.31 0.31 0.30 0.29 0.27 Product (pour point) Mass composition of mixtures RVR 2 (not measurable) 90 80 70 60 35 FAME 0 (-12°C) 10 20 30 40 65 Characteristic Unit Analysis Viscosity at 50°C measured mm ² /s 1361 347.5 124.2 54.43 13.08 V50 calculated 1982 565.2 198.0 82.15 15.90 deviation in % vs measurement -46 -63 -59 -51 -22 Reproducibility (%) 7.4 7.4 7.4 7.4 7.4 Viscosity at 100°C measured mm ² /s 80.13 36.61 19.52 11.62 4,391 V100 calculated 94.24 44.76 23.79 13.87 4.84 deviation in % vs measurement -18 -22 -22 -19 -10 Reproducibility (%) 4 5 6 7 11 Density at 15°C measured kg/ ^m3 984.4 971.6 959.5 947.5 919.6 CCIC - 833 833 833 832 830 Pour point °C 0 -18 -30 -33 -30 S-value measured S 2.05 2.28 2.26 2.36 2.42 Her 0.62 0.61 0.61 0.61 0.62 So 0.77 0.89 0.89 0.93 0.93 Calculated S-value S 1.94 1.83 1.72 1.61 1.35 Her 0.62 0.62 0.62 0.62 0.62 So 0.74 0.69 0.65 0.61 0.50 Difference between measured and calculated S-value 0.11 0.45 0.54 0.75 1.07 Reproducibility of the method on the measured S-value 0.33 0.35 0.35 0.36 0.36 Product (pour point) Mass composition of mixtures RSV (not measurable) 411-469 80.0 80.0 70.0 70.0 70.0 FAME 0 (-12°C) 410-321 20.0 0.0 30.0 0.0 0.0 GO (0°C) 411-393 0.0 20.0 0.0 30.0 0.0 UCOME (3°C) 411-241 30.0 Characteristic Unit Analysis Viscosity at 50°C (measured) mm ² /s 223.4 269.5 95.11 113.3 98.69 V50 calculated 297 276 123 112.3 127.1 deviation in % vs measurement -33 -2 -29 1 -29 Reproducibility (%) 7.4 7.4 7.4 7.4 7.4 Viscosity at 100°C (measured) mm ² /s 28.29 30.28 16.69 17.37 16.96 V100 calculated 30.6 28.1 17.9 16 18.2 deviation in % vs measurement -8 7 -7 8 -7 Reproducibility (%) 5 5 6 6 6 Density at 15°C kg/ ^m3 961.9 956.6 951.4 943.1 952.1 CCIC - 829 821 829 818 829 Pour point °C -24 -3 -24 -9 -9 S-value measured S 5.84 4.88 5.50 4.88 6.01 Her 0.87 0.86 0.88 0.85 0.85 So 0.75 0.67 0.67 0.72 0.89 Calculated S-value S 5.75 5.64 5.50 5.25 5.43 Her 0.88 0.88 0.88 0.88 0.88 So 0.69 0.68 0.65 0.63 0.65 Difference between measured and calculated S-value 0.09 -0.76 0.08 -0.37 0.58 Reproducibility of the method on the measured S-value 0.70 0.61 0.67 0.61 0.72 Product (pour point) Mass composition of mixtures RATE (36°C) 411-338 80.0 80.0 70.0 70.0 70.0 70.0 FAME 0 (-12°C) 410-321 20.0 0.0 30.0 0.0 FAME 1 (0°C) 410-308 30.0 FAME 2 (-6°C) 410-182 30.0 GO (0°C) 411-393 0.0 20.0 0.0 30.0 Characteristic Unit Analysis Viscosity at 50°C (measured) mm ² /s 50.09 57.1 29.44 33.34 28.17 29.55 V50 calculated 64.3 60.9 38.6 35.9 36.93 38.54 deviation in % vs measurement -28 -7 -31 -8 -31 -30 Viscosity at 100°C (measured) mm ² /s 9,535 9,814 6.937 7,066 6,759 6.925 V100 calculated 10.6 10 7.9 7.2 7,703 7.7886 deviation in % vs measurement -11 -2 -14 -2 -14 -12 Density at 15°C kg/ ^m3 936.6 931.3 929.4 921.6 930.2 929.3 CCIC - Pour point °C 36 33 33 30 33 33 Calculated pour point 33 33 31 31 32 31

Tables 3 to 7 show differences between the measured and calculated viscosities (at 50° C. and 100° C.) that are higher for the bases containing FAME or UCOME compared to the bases containing GO as fluxing agent. This deviation is also much higher for the bases containing a visbroken residue than for the bases containing the other residues.

Note that the reproducibility of the viscosity measurement is 7.4% at 50°C. The percentage differences between the measured and calculated viscosities are of this order of magnitude for the bases containing GO and beyond for the bases containing FAME or UCOME, and very much beyond for the bases containing a residue visbreaked by compared to bases containing other types of residues.

Similarly for the viscosity at 100°C, it is observed that the percentage differences between the measured and calculated viscosities are lower than the reproducibility for the bases containing GO, beyond that for the bases containing FAME or UCOME, and far beyond for the bases containing a visbreaked residue compared to the bases containing other types of residues.

With regard to the pour point, it should be noted that the pour point of an RVR is not measurable. Nevertheless, the difference between the pour point of the base and that of the flux contained in the base is higher in absolute value for the RVR bases with FAME than for the RVR bases with GO. Moreover, it is observed that this difference increases with the flux content, and is higher for FAME contents of 30 to 40% m/m. For the bases containing an RSV, a similar but less pronounced behavior is observed, with a difference between the pour point of the base and that of the fluxing agent contained in the base, which is higher in absolute value for the RSV bases with FAME or UCOME than for RSV bases with GO.

The mixing law correctly predicts the S-value parameters of the RVR/GO bases. On the other hand, the measured S-value of the bases with the FAME increases with the % of FAME which should not be the case the FAME being paraffinic compounds. The mixing law also predicts a decrease in the S-value. These deviations are very much greater than the reproducibility of the method and come from the aromaticity So of the matrix: the measurements clearly show that the Sa is constant whatever the mixture (the Sa of the RVR is not modified since the fluxes do not introduce asphaltenes).

A good agreement is observed between S-value and So measured and calculated for the RVR/GO bases whereas for the RVR/EMAG bases the S-value and the aromaticity So increase while the mixing law predicts a decrease.

The examples in Tables 4 and 5 with visbroken residue thus show that the difference between the measured and calculated S-value is lower than the reproducibility for the mixtures with GO and much higher for the mixtures with FAME (except for the 90% RVR mixture / 10% FAME).

The examples in Table 6 show that the difference between the measured and calculated S-value is less than the reproducibility for all the mixtures except the 80% RSV/20% GO mixture. However the measured S-value of the mixtures with GO is lower than the calculated S-value whereas once again the measured S-value of the mixtures with FAME is higher than the calculated S-value.

These observations lead to attributing to FAME a booster effect on the viscosity (decrease), the pour point (decrease) and the stability (increase) of a mixture with a residue. This booster effect is also more pronounced for bases containing visbroken residues.

Table 8 below summarizes the properties of fuel mixtures that can be used as marine fuels. A difference is observed between the measured viscosity and the calculated viscosity, the measured viscosity being much lower than the calculated viscosity, and this all the more so for the mixtures containing a visbroken residue. Table 8: Combustible mixtures Product (pour point) Mass composition of mixtures RVR 1 (not measurable) 411-392 85.0 70.0 60.0 RSV (not measurable) 70.0 RATE (36°C) 70.0 FAME 0 (-12°C) 410-321 10.0 20.0 20.0 20.0 20.0 GO (0°C) 411-393 5.0 10.0 20.0 10.0 10.0 UCOME (3°C) 410-241 Analysis Unit Viscosity at 50°C (measured) mm ² /s 428.3 98.92 48.05 98.16 30.53 V50 calculated 675.1 149.0 65.0 119 37.7 deviation in vs measure -58 -51 -35 -21 -23 Reproducibility (%) 7.4 7.4 7.4 7.4 - Viscosity at 100°C (measured) mm ² /s 39.91 16.18 10.07 16.33 6,948 V100 calculated 48.1 19.3 11.5 17.2 7.7 deviation in vs measurement -21 -19 -14 -5 -11 Reproducibility (%) 5 6 7 6 - Density at 15°C kg/ ^m3 974.8 955.6 941.6 948 926.7 CCIC - 835 832 828 825 Pour point °C -12 -21 -15 -18 30 S-value measured S 1.70 1.73 1.62 5.78 Her 0.56 0.55 0.55 0.85 So 0.75 0.78 0.73 0.86 Calculated S-value S 1.53 1.40 1.30 4.73 Her 0.56 0.56 0.56 0.88 So 0.67 0.62 0.57 0.57 Difference between measured and calculated S-value 0.17 0.23 0.32 1.05

Claims (14)

Use of alkyl esters of fatty acids to improve the viscosity of a component of at least one hydrocarbon residue, in which there is mixed (i) 10 to 70% m/m of a first component of alkyl esters of fatty acids of renewable origin with (ii) 90% to 30% m/m of a second component of at least one hydrocarbon residue, and in which the mixture obtained has a kinematic viscosity lower than a kinematic viscosity calculated according to the formula: $$\vartheta =\exp \left(\exp \left(\frac{{\mathit{VB}}_{\mathit{blend}}-\mathrm{23,097}}{\mathrm{33,469}}\right)\right)-0.8$$

where VB _mixture is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated by means of the formula: VB _i = 23.097 + 33.469 × Log ( Log ( v _i + 0.8)) (5), where v _i is the kinematic viscosity of component i expressed in stokes. Use according to Claim 1, in which the at least one hydrocarbon residue is chosen from an atmospheric residue, a vacuum residue and a visbreaking residue. Use according to claim 1, wherein the at least one hydrocarbon residue is selected from vacuum residue and visbreaking residue. Use according to claim 1, wherein the at least one hydrocarbon residue is a visbreaking residue. Use according to claim 3 or 4, in which the mixture obtained has a measured S-value greater than a calculated S-value S _mixture , defined as being equal to: $$S_{\mathit{blend}}=\frac{{\mathit{So}}_{\mathit{blend}}}{1-{\mathit{Her}}_{\mathit{blend}}}$$

with, $${\mathit{So}}_{\mathit{blend}}={\displaystyle \sum x_I\times {\mathit{So}}_I}$$

Or $${\mathit{So}}_{\mathit{blend}}=\frac{{\displaystyle \sum x_I\times \left(100-{\mathit{ASP}}_I\right)\times {\mathit{So}}_I}}{{\displaystyle \sum x_I\times \left(100-{\mathit{ASP}}_I\right)}}$$

$${\mathit{Her}}_{\mathit{blend}}=\frac{{\displaystyle \sum x_I\times {\mathit{ASP}}_I\times {\mathit{Her}}_I}}{{\displaystyle \sum x_I\times {\mathit{ASP}}_I}}$$

Or : x _i is the mass fraction of component i, ASP _i is the asphaltenes content (%m) of component i, So _i is the solvent power of component i, Sa _i is the peptizability of component i, and the solvent power of the first component is estimated from a correlation expressing the solvent power So of said first component as a function of the kinematic viscosity at 50° C., the kinematic viscosity at 100°C and the density at 15°C of said first component. Use according to any one of claims 1 to 5, wherein the first component comprises methyl esters, ethyl esters, propyl esters and mixtures thereof. Base for marine fuel comprising: (i) 10 to 70 m/m of a first component of fatty acid alkyl esters of renewable origin, (ii) 90 to 30% m/m of a second component of at least one hydrocarbon residue, said base having a kinematic viscosity lower than a kinematic viscosity calculated according to the formula: $$\vartheta =\exp \left(\exp \left(\frac{{\mathit{VB}}_{\mathit{blend}}-\mathrm{23,097}}{\mathrm{33,469}}\right)\right)-0.8$$

where VB _mixture is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated by means of the formula: VB _i = 23.097 + 33.469 × Log ( Log ( v _i + 0.8)) (5), where v _i is the kinematic viscosity of component i expressed in stokes. Base according to any one of Claim 7, in which the at least one hydrocarbon residue of the second component is chosen from an atmospheric residue, a vacuum residue and a visbreaking residue. Base according to any one of Claim 7, in which the at least one hydrocarbon residue of the second component is chosen from a vacuum residue and a visbreaking residue. Base according to any one of Claim 7, in which the at least one hydrocarbon residue of the second component is a visbreaking residue. Base according to claim 9 or 10 having a measured S-value greater than a calculated S-value S _mixture , defined as being equal to: $$S_{\mathit{blend}}=\frac{{\mathit{So}}_{\mathit{blend}}}{1-{\mathit{Her}}_{\mathit{blend}}}$$

with, $${\mathit{So}}_{\mathit{blend}}={\displaystyle \sum x_I\times {\mathit{So}}_I}$$

Or $${\mathit{So}}_{\mathit{blend}}=\frac{{\displaystyle \sum x_I\times \left(100-{\mathit{ASP}}_I\right)\times {\mathit{So}}_I}}{{\displaystyle \sum x_I\times \left(100-{\mathit{ASP}}_I\right)}}$$

$${\mathit{Her}}_{\mathit{blend}}=\frac{{\displaystyle \sum x_I\times {\mathit{ASP}}_I\times {\mathit{Her}}_I}}{{\displaystyle \sum x_I\times {\mathit{ASP}}_I}}$$

Or : x _i is the mass fraction of component i, ASP _i is the asphaltene content (%m/m) of component i, So _i is the solvent power of component i, Sa _i is the peptizability of component i, and the solvent power of the first component is estimated from a correlation expressing the solvent power So of said first component as a function of the kinematic viscosity at 50°C, the kinematic viscosity at 100°C and the density at 15°C of said first component. Base according to any one of claims 7 to 11, in which the component of fatty acid alkyl esters of renewable origin comprises methyl esters, ethyl esters, propyl esters and mixtures thereof. Marine fuel comprising a base according to any one of Claims 7 to 12, and optionally at least one fluxing agent of petroleum origin. A method of improving the viscosity of a component of at least one hydrocarbon residue comprising mixing (i) 10 to 70% m/m of a first component of fatty acid alkyl esters of renewable with (ii) 90% to 30% m/m of a second component of at least one hydrocarbon residue, and in which the mixture obtained has a kinematic viscosity lower than a kinematic viscosity calculated according to the formula: $$\vartheta =\exp \left(\exp \left(\frac{{\mathit{VB}}_{\mathit{blend}}-\mathrm{23,097}}{\mathrm{33,469}}\right)\right)-0.8$$

where VB _mixture is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated by means of the formula: $${\mathit{VB}}_I=\mathrm{23,097}+\mathrm{33,469}\times \mathit{Log}\left(\mathit{Log}\left(v_I+0.8\right)\right)$$

where v _i is the kinematic viscosity of component i expressed in stokes.