MARINE FUEL BASE COMPRISING A COMPONENT OF RENEWABLE ORIGIN AND METHOD FOR MANUFACTURING SAME

Abstract

A marine fuel base comprising an alkyl ester component of renewable origin, derived from fatty acids of plant or animal origin, which improves the viscosity and stability of a petroleum residuum, especially a visbroken residuum.

Claims

1. Use of fatty acid alkyl esters to improve the viscosity of a component of at least one hydrocarbon residue and obtain a marine fuel base, wherein (i) 10 to 70% m/m of a first component consisting of fatty acid alkyl esters of renewable origin is mixed with (ii) 90% to 30% m/m of a second component consisting of at least one hydrocarbon residue coming from a crude oil chosen from an atmospheric residue, a vacuum residue and a visbreaking residue, and the mixture obtained forms a marine fuel base that has a kinematic viscosity at 50 C. 15 to 75% lower than a kinematic viscosity calculated according to the formula: $\begin{array}{cc}=\exp \left(\exp \left(\frac{V{B}_{\mathrm{mlange}}-23.097}{33.469}\right)\right)-0.8,& \left(4\right)\end{array}$ where VB.sub.mlange is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated via the formula: $\begin{array}{cc}V{B}_i=23.097+33.469\ln \left(\ln \left(v_i+0.8\right)\right),& \left(5\right)\end{array}$ where v.sub.i is the kinematic viscosity of the component i expressed in stokes.

2. Use according to claim 1, wherein the mixture obtained has a kinematic viscosity at 100 C. 5 to 30% lower than the calculated viscosity.

3. Use according to claim 1, wherein the at least one hydrocarbon residue chosen from a vacuum residue and a visbreaking residue.

4. Use according to claim 1, wherein the at least one hydrocarbon residue is a visbreaking residue.

5. Use according to claim 3 or 4, to obtain a mixture having an S-value measured according to the standard ASTM D7157-18 (2018 Revision) greater than a calculated S-value S.sub.mlange, defined as being equal to: $\begin{array}{cc}{S}_{\mathrm{mlange}}=\frac{{\mathrm{So}}_{\mathrm{mlange}}}{1-{\mathrm{Sa}}_{\mathrm{mlange}}},& \left(3\right)\end{array}$ with, $\begin{array}{cc}{\mathrm{So}}_{\mathrm{mlange}}=.Math.x_{i}S{o}_i& \left(1\right)\end{array}$ $\begin{array}{cc}\mathrm{or}{\mathrm{So}}_{\mathrm{mlange}}=\frac{x_i\left(100-AS{P}_i\right)S{o}_i}{x_i\left(100-AS{P}_i\right)},& \left(1\mathrm{bis}\right)\end{array}$ $\begin{array}{cc}{\mathrm{Sa}}_{\mathrm{mlange}}=\frac{x_{i}AS{P}_{i}S{a}_i}{x_{i}AS{P}_i}& \left(2\right)\end{array}$ where: the parameters So and Sa are as defined in the standard ASTM D7157-18 (2018 Revision), and x.sub.i is the mass fraction of the component i, ASP.sub.i is the content of asphaltenes (% m) of the component i, So.sub.i is the solvent power of the component i, Sa.sub.i is the peptizability of the component i, and the solvent power of the first component is estimated from a correlation expressing the solvent power So of said first component according to the kinematic viscosity at 50 C., the kinematic viscosity at 100 C. and the density at 15 C. of said first component.

6. Use according to claim 1, wherein the first component comprises methyl esters, ethyl esters, propyl esters and the mixtures thereof.

7. Marine fuel base comprising: (i) 10 to 70% m/m of a first component consisting of fatty acid alkyl esters of renewable origin, (ii) 90 to 30% m/m of a second component consisting of at least one hydrocarbon residue coming from a crude oil chosen from an atmospheric residue, a vacuum residue and a visbreaking residue, said base having a kinematic viscosity at 50 C. 15 to 75% lower than a kinematic viscosity calculated according to the formula: $\begin{array}{cc}=\exp \left(\exp \left(\frac{V{B}_{\mathrm{mlange}}-23.097}{33.469}\right)\right)-0.8& \left(4\right)\end{array}$ where VB.sub.mlange is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated via the formula: $\begin{array}{cc}V{B}_i=23.097+33.469\ln \left(\ln \left(v_i+0.8\right)\right),& \left(5\right)\end{array}$ where v.sub.i is the kinematic viscosity of the component i expressed in stokes.

8. Base according to claim 7, having a kinematic viscosity at 100 C. 5 to 30% lower than the calculated viscosity.

9. Base according to claim 7, wherein the at least one hydrocarbon residue of the second component is chosen from a vacuum residue and a visbreaking residue.

10. Base according to claim 7, wherein the at least one hydrocarbon residue of the second component is a visbreaking residue.

11. Base according to claim 9 having an S-value measured according to the standard ASTM D7157-18 (2018 Revision) greater than a calculated S-value S.sub.mlange, defined as being equal to: $\begin{array}{cc}{S}_{\mathrm{mlange}}=\frac{{\mathrm{So}}_{\mathrm{mlange}}}{1-{\mathrm{Sa}}_{\mathrm{mlange}}},& \left(\mathrm{equation}3\right)\end{array}$ with, $\begin{array}{cc}{\mathrm{So}}_{\mathrm{mlange}}=.Math.x_{i}S{o}_i& \left(\mathrm{equation}l\right)\end{array}$ $\begin{array}{cc}\mathrm{or}{\mathrm{So}}_{\mathrm{mlange}}=\frac{x_i\left(100-AS{P}_i\right)S{o}_i}{x_i\left(100-AS{P}_i\right)},& \left(\mathrm{equation}l\mathrm{bis}\right)\end{array}$ $\begin{array}{cc}{\mathrm{Sa}}_{\mathrm{mlange}}=\frac{x_{i}AS{P}_{i}S{a}_i}{x_{i}AS{P}_i}& \left(\mathrm{equation}2\right)\end{array}$ where: the parameters So and Sa are as defined in the standard ASTM D7157-18 (2018 Revision), and x.sub.i is the mass fraction of the component i, ASP.sub.i is the content of asphaltenes (% m/m) of the component i, So.sub.i is the solvent power of the component i, Sa.sub.i is the peptizability of the component i, and the solvent power of the first component is estimated from a correlation expressing the solvent power So of said first component according to the kinematic viscosity at 50 C., the kinematic viscosity at 100 C. and the density at 15 C. of said first component.

12. Base according to claim 7, wherein the component of fatty acid alkyl esters of renewable origin comprises methyl esters, ethyl esters, propyl esters and the mixtures thereof.

13. Marine fuel comprising a base according to claim 7, and optionally at least one fluxant of petroleum origin.

14. Method for improving the viscosity of a component of at least one hydrocarbon residue for the preparation of a marine fuel base comprising the mixture of (i) 10 to 70% m/m of a first component consisting of fatty acid alkyl esters of renewable origin with (ii) 90% to 30% m/m of a second component consisting of at least one hydrocarbon residue coming from a crude oil chosen from an atmospheric residue, a vacuum residue and a visbreaking residue, and for obtaining a mixture forming a marine fuel base that has a kinematic viscosity at 50 C. 15 to 75% lower than a kinematic viscosity calculated according to the formula: $\begin{array}{cc}=\exp \left(\exp \left(\frac{V{B}_{\mathrm{mlange}}-23.097}{33.469}\right)\right)-0.8,& \left(4\right)\end{array}$ where VB.sub.mlange is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated via the formula: $\begin{array}{cc}V{B}_i=23.097+33.469\ln \left(\ln \left(v_i+0.8\right)\right),& \left(5\right)\end{array}$ where v.sub.i is the kinematic viscosity of the component i expressed in stokes.

Description

DETAILED DESCRIPTION

[0046] A first object of the invention relates to the use of fatty acid alkyl esters to improve the viscosity of a component of at least one hydrocarbon residue, wherein (i) 10 to 70% m/m of a first component of fatty acid alkyl esters of renewable origin is mixed with (ii) 90% to 30% m/m of a second component of at least one hydrocarbon residue, and wherein the mixture obtained has a kinematic viscosity lower than a kinematic viscosity calculated according to the formula:

[00003]$\begin{array}{cc}=\exp \left(\exp \left(\frac{{\mathrm{VB}}_{\mathrm{mlange}}-23.097}{33.469}\right)\right)-0.8& \left(4\right)\end{array}$

where VB.sub.mlange is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated via the formula:

[00004]$\begin{array}{cc}{\mathrm{VB}}_i=23.097+33.469\ln \left(\ln \left(v_i+0.8\right)\right),& \left(5\right)\end{array}$

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

[0047] These various formulas (4) (5) correspond to the Refutas method (Maples, R. E., 2000, Petroleum Refinery Process Economics, PennWell, ISBN 978-0-87814-779-3).

[0048] In one embodiment, the mixture obtained can have a measured S-value greater than a calculated S-value S.sub.mlange, previously defined in 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 according to the kinematic viscosity at 50 C., the kinematic viscosity at 100 C. and the density at 15 C. of said first component. This correlation can be established by following the teaching of the document WO 2021/122349 A1.

[0049] The fatty acid alkyl esters can thus be used to manufacture a marine fuel base having an improved viscosity. In other words, these fatty acid alkyl esters can be used to manufacture a mixture that can form a marine fuel base or a marine fuel.

[0050] Thus, another object of the invention relates to a marine fuel base comprising: [0051] (i) 10 to 70% m/m of a first component of fatty acid alkyl esters of renewable origin, [0052] (ii) 90 to 30% m/m of a second component of at least one hydrocarbon residue, [0053] said base having a kinematic viscosity lower than a kinematic viscosity calculated according to the formula:

[00005]$\begin{array}{cc}=\exp \left(\exp \left(\frac{V{B}_{\mathrm{mlange}}-23.097}{33.469}\right)\right)-0.8& \left(4\right)\end{array}$ [0054] where VB.sub.mlange is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated via the Refutas formula: VB.sub.i=23.097+33.469Ln(Ln(v.sub.i+0.8)) (5) where v.sub.i is the kinematic viscosity of the component i expressed in stokes.

[0055] The use of the component of fatty acid alkyl esters can thus allow to obtain a mixture having a kinematic viscosity at 50 C. 15 to 75% lower than the calculated viscosity. This lowering of the kinematic viscosity is particularly significant when the component of fatty acid alkyl esters is added to a visbreaking residue or to a mixture of visbreaking residues, with a 20 to 70% reduction in the viscosity with respect to the calculated viscosity whereas it is 15 to 40% for the other residues (at equal content of component of alkyl esters).

[0056] The use of the component of fatty acid alkyl esters can also allow to obtain a mixture having a kinematic viscosity at 100 C. 5 to 30% lower than the calculated viscosity. This lowering of the kinematic viscosity is also greater when the component of fatty acid alkyl esters is added to a visbreaking residue or to a mixture of visbreaking residues, with a 10 to 30% reduction in the viscosity with respect to the calculated viscosity whereas it is 5 to 20% for the other residues (at equal content of component of alkyl esters).

[0057] Thus, surprisingly, the component of fatty acid alkyl esters acts as a fluxant for the second component, producing an effect on the viscosity that is greater than the expected effect. The first component can thus be advantageously used as a fluxant for the preparation of a marine fuel base. In particular, the reduction of the viscosity obtained by addition of the first component is a certain advantage, since the temperatures of use can be significantly reduced.

[0058] Moreover, when the second component is at least one hydrocarbon residue chosen from a vacuum residue and a visbreaking residue, it was observed in a surprising manner that the fatty acid alkyl esters have an effect on the pour point of the mixture (typically determined according to the standard ISO 3016-2019) greater than the effect provided by fluxants 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 first component of the mixture, this difference being greater in absolute value than the difference in absolute value between the pour point of a fluxant of petroleum origin and the pour point of a mixture of this fluxant of petroleum origin with the second component (in other words, for a mixture in which the first component has been replaced by a fluxant of petroleum origin). This effect is greater for the visbreaking residues than for the vacuum residues.

[0059] Advantageously, when the second component is at least one hydrocarbon residue chosen from a vacuum residue and a visbreaking residue, the marine fuel base can have a measured S-value greater than a calculated S-value S.sub.mlange as defined above, by using a value of the solvent power of the first component estimated from a correlation expressing the solvent power So of said first component according to the kinematic viscosity at 50 C., the kinematic viscosity at 100 C. and the density at 15 C. of said first component.

[0060] Finally, the object of the invention is a marine fuel comprising a marine fuel base according to the invention and optionally at least one fluxant of petroleum origin.

[0061] Because of the effect on the viscosity of the component of alkyl esters, the base according to the invention allows to manufacture a marine fuel requiring a reduced, or even null, quantity of fluxant of petroleum origin.

[0062] The object of the invention is also a method 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 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 wherein the mixture obtained has a viscosity lower than a viscosity calculated according to the formula:

[00006]$\begin{array}{cc}=\exp \left(\exp \left(\frac{V{B}_{\mathrm{mlange}}-23.097}{33.469}\right)\right)-0.8& \left(4\right)\end{array}$ [0063] where VB.sub.mlange is the weighted average of the viscosity indices of the first component and of the second component, these viscosity indices being calculated via the Refutas formula:

[00007]$\begin{array}{cc}V{B}_i=23.097+33.469\ln \left(\ln \left(v_i+0.8\right)\right),& \left(5\right)\end{array}$ [0064] where v.sub.i is the kinematic viscosity of the component i expressed in stokes.

[0065] This method thus allows to prepare a mixture forming a marine fuel base having one or more of the features described above.

First component of alkyl esters

[0066] 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 the oils/fats with an alcohol to produce a fatty acid ester and glycerin is known by the name transesterification. Alternatively, the fatty acid alkyl esters can be produced by the reaction of a fatty acid with an alcohol (esterification reaction) to form a fatty acid ester.

[0067] The first component is thus exclusively of biological origin: this will be called component of renewable origin.

[0068] The vegetable oils can be chosen from pine oil, colza 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, cotton oil, corn oil, palm kernel oil, soybean oil, squash oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, China wood oil, rice oil, safflower oil, algae oil, used oils, and any combination thereof.

[0069] The used oils comprise used cooking oils (used food oils) and oils recovered from wastewater, such as trapped and drained fats/oils, gutter oils, sewer oils, for example from wastewater treatment plants, and used fats from the food industry.

[0070] The animal fats can be chosen from tallow, lard, fat (yellow and brown fat), fish oils/fats, the fat of milk and any combination thereof.

[0071] The alcohol can be chosen from the 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.

[0072] In a preferred embodiment, the component of alkyl esters comprises, or consists of, methyl esters, ethyl esters, propyl esters, alone or in a mixture, preferably methyl esters, ethyl esters, alone or in a mixture, for example methyl esters. In a preferred embodiment, the component of alkyl esters thus consists only of alkyl esters, in particular methyl esters, ethyl esters and/or propyl esters, preferably methyl esters and/or ethyl esters, without another component in particular of the alcohol type.

Second component of at least one hydrocarbon residue

[0073] The at least one hydrocarbon residue of the second component can be chosen from a residue coming from a distillation process or a residue coming from a visbreaking process.

[0074] The residue coming from the distillation process can be an atmospheric residue or a vacuum residue.

[0075] In one embodiment, the second component is at least one hydrocarbon residue chosen from a vacuum residue and a visbreaking residue.

[0076] In a preferred embodiment, the at least one hydrocarbon residue of the second component is a visbreaking residue.

[0077] The second component is thus exclusively of petroleum origin, coming from a crude oil. In particular, the at least one residue is not a residue coming from shale oil.

[0078] Advantageously, the second component can consist of at least one hydrocarbon residue, in particular as described above.

[0079] Advantageously, the at least one hydrocarbon residue of the second component can 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.

[0080] Advantageously, the at least one hydrocarbon residue of the second component can have a density at 15 C. of 845 to 1060 kg/m.sup.3 and/or a viscosity at 100 C. of 10 to 2500 mm.sup.2/s.

[0081] In one embodiment, the at least one hydrocarbon residue of the second component can have a density at 15 C. of 950 to 1060 kg/m.sup.3 and/or a viscosity at 100 C. of 20 to 2500 mm.sup.2/s.

[0082] When the residue is a vacuum residue, it can have at least one of the following features: [0083] for a sulfur content of at most 1.5% m/m, preferably of at most 1% m/m: [0084] a content of asphaltenes lower than 3% m/m, [0085] a carbon residue of less than 15% m/m, [0086] regardless of the sulfur content, a value Sa greater than 0.75, [0087] regardless of the sulfur content, a density at 15 C. of 950 to 1000 kg/m.sup.3, [0088] regardless of the sulfur content, a viscosity at 100 C. of 20 to 2500 mm.sup.2/s, [0089] regardless of the sulfur content, a viscosity at 50 C. of 150 to 600000 mm.sup.2/s.

[0090] When the residue is a visbreaking residue, it can have at least one of the following features: [0091] for a sulfur content of at most 1.5% m/m, preferably of at most 1% m/m: [0092] a content of asphaltenes greater than 3% m/m, [0093] a carbon residue greater than 15% m/m, [0094] regardless of the sulfur content, a value Sa lower than 0.70, [0095] regardless of the sulfur content, a density at 15 C. of 950 to 1060 kg/m.sup.3, [0096] regardless of the sulfur content, a viscosity at 100 C. of 80 to 1500 mm.sup.2/s, [0097] regardless of the sulfur content, a viscosity at 50 C. of 1700 to 300000 mm.sup.2/s.

[0098] When the residue is an atmospheric residue, it can have at least one of the following features: [0099] a density at 15 C. of 845 to 990 kg/m.sup.3, [0100] a viscosity at 100 C. of 10 to 180 mm.sup.2/s, [0101] a viscosity at 50 C. of 50 to 6200 mm.sup.2/s.

Marine Fuel Base

[0102] The marine fuel base 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, and thus without any other component in particular of the alcohol type.

[0103] In one embodiment, the base can contain the first component in a content of 10 to 60% m/m, of 10 to 50% m/m, of 10 to 50% m/m or in any range defined by two of these limits, the rest of the base consisting of the second component.

[0104] The content of first component in the base according to the invention, and in particular of methyl esters, can be determined by the testing methods IP579 or ASTM D7963, as described in the standard ISO 8217-2018.

[0105] The base according to the invention can be obtained by simple mixture of the first and second components described above.

[0106] In order to facilitate their mixture, 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 a suitable preheating temperature.

[0107] The marine fuel base can have one or more of the following features: [0108] a density of 860 to 991 kg/m.sup.3 at 15 C., [0109] a sulfur content less than or equal to 0.7% by mass, [0110] a pour point of at most 42 C., [0111] a CCAI of at most 870, [0112] a kinematic viscosity at 50 C. of at most 2000 mm.sup.2/s, [0113] a flash point of at least 60 C.

[0114] When the second component of the marine fuel base comprises only, or even consists of, one or more atmospheric residues, the base can have one or more of the following features: [0115] a density at 15 C. of 900 to 980 kg/m.sup.3 or of 920 to 960 kg/m.sup.3, or in any interval defined by two of these limits, [0116] a sulfur content less than or equal to 0.7% by mass, [0117] a pour point of at most 42 C., typically from 25 to 42 C., [0118] a CCAI of at most 870, [0119] a kinematic viscosity at 50 C. of at most 80 mm.sup.2/s, typically from 25 to 80 mm.sup.2/s, [0120] a flash point of at least 60 C.

[0121] When the second component of the marine fuel base comprises only, or even consists of, one or more vacuum residues, the base can have one or more of the following features: [0122] a density at 15 C. of 930 to 980 kg/m.sup.3 or of 940 to 970 kg/m.sup.3, or in any interval defined by two of these limits, [0123] a sulfur content less than or equal to 0.7% by mass, [0124] a pour point of at most 12 C. or of at most 0 C., for example from 6 to 30 C., [0125] a CCAI of at most 860, [0126] a kinematic viscosity at 50 C. of at most 380 mm.sup.2/s, for example from 50 to 380 mm.sup.2/s, [0127] an S-value greater than 3, typically from 3 to 7, [0128] a flash point of at least 60 C.

[0129] When the second component of the marine fuel base comprises only, or even consists of, one or more visbreaking residues, the base can have one or more of the following features: [0130] a density at 15 C. of 910 to 991 kg/m.sup.3, [0131] a sulfur content less than or equal to 0.7% by mass, [0132] 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, [0133] a CCAI of at most 870 or of at most 840, for example from 820 to 870, [0134] a kinematic viscosity at 50 C. of at most 2000 mm.sup.2/s, for example from 25 to 2000 mm.sup.2/s, [0135] 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, [0136] a flash point of at least 60 C.

Marine Fuel

[0137] The base according to the invention can be used as a base for manufacturing a marine fuel. Marine fuel means a fuel having specifications suitable for a use in the diesel engines and boilers of ships, before any conventional treatment on board (settling, centrifugation, filtration) before its use. This type of fuel can also be used in stationary diesel engines, of a type identical or similar to those used for marine uses.

[0138] For this purpose, the base according to the invention is typically mixed with a fluxant of petroleum origin. However, it can also be used alone as a marine fuel. The marine fuel according to the invention can in particular respect all the specifications of the marine fuels presented in the standard ISO 8217-June 2018, except for the content of FAME or other methyl esters.

[0139] The marine fuel can in particular respect the specifications of the fuels of the type RMD, RME, RMG, RMK of the standard (except for the content of methyl esters).

[0140] This fluxant of petroleum origin is for example chosen from: [0141] the gasoils coming from the direct distillation of petroleum: kerosene, lamp oil, light gasoil, medium gasoil, heavy gasoil, [0142] the products of vacuum distillation of the atmospheric residue: vacuum light gasoil, vacuum medium gasoil, vacuum heavy gasoil, distillate, [0143] the products of atmosphere or vacuum distillation of the effluents of the conversion units: visbreaking gasoil, visbreaking distillate, [0144] the products coming from the catalytic cracking units and from the desulfurization and hydrodesulfurization units: catalytic cracker gasoil (LCO), heavy catalytic cracker gasoils (HCO, bright oil, Slurry), desulfurized gasoil, gasoil and bleed (residue) from the hydrodesulfurization units, [0145] the products coming from the steam-cracking units: pyrolysis oil or gasoline.

[0146] The characteristics of the marine fuel such as its viscosity, its density and its sulfur content can be adjusted by varying the proportions of fluxant of petroleum origin and of marine fuel base according to the invention.

[0147] Typically, the content of fluxant of petroleum origin of the marine fuel can be from 0 to 30% m/m, preferably from 0 to 20% m/m, the rest consisting of the marine fuel base according to the invention.

[0148] In one embodiment, the marine fuel according to the invention can have a content of first component of fatty acid alkyl esters of 7 to 38% m/m, a content of second component of at least one residue of 42 to 85.5% m/m and a content of fluxant of petroleum origin of 0 to 30% m/m.

[0149] In another embodiment, the marine fuel according to the invention can have a content of first component of fatty acid alkyl esters of 8 to 38% m/m, a content of second component of at least one residue of 48 to 72% m/m and a content of fluxant of petroleum origin of 0 to 20% m/m.

[0150] The marine fuel according to the invention can in particular have one or more of the following features: [0151] 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 in any interval defined by two of these limits, [0152] a density at 15 C. of at most 1010 kg/m.sup.3, of at most 991 kg/m.sup.3, of at most 975 kg/m.sup.3, of at most 960 kg/m.sup.3, of at most 920 kg/m.sup.3, of at most 900 kg/m.sup.3 or of at most 890 kg/m.sup.3, in particular greater than 900 kg/m.sup.3, or in any interval defined by two of these limits, [0153] a pour point of at most 30 C., of at most 6 C., of at most 0 C. or of at most 6 C., in particular greater than 42 C., or in any interval defined by two of these limits, [0154] a kinematic viscosity at 50 C. of at most 700 mm.sup.2/s, of at most 500 mm.sup.2/s, of at most 380 mm.sup.2/s, of at most 180 mm.sup.2/s, of at most 80 mm.sup.2/s, of at most 30 mm.sup.2/s or of at most 10 mm.sup.2/s, in particular greater than 2 mm.sup.2/s, or in any interval defined by two of these limits, [0155] a flash point of at least 60 C.

[0156] The invention allows in particular to formulate a marine fuel with a very low sulfur content (less than 0.50% sulfur), comprising a renewable component.

EXAMPLES

[0157] Various bases for a marine fuel were prepared, each comprising a residue (atmospheric residue, vacuum residue or visbreaking residue according to the trials) and a fluxant of petroleum origin or of biological origin.

[0158] The residues used are visbreaking residues (noted as RVR), a vacuum residue (noted as RSV) and an atmospheric residue (noted as RAT). The fluxants of renewable origin tested are fatty acid methyl esters coming from the transesterification of vegetable oils (noted as FAME 0, FAME 1 and FAME 2) and fatty acid methyl esters coming from the transesterification of cooking oils (noted as UCOME). The fluxant of petroleum origin is a diesel (noted as GO).

[0159] The characteristics of the various components used for the bases are grouped together in tables 1 (residues) and 2 (fluxants).

[0160] All the analyses presented in tables 2 to 8 were carried out by following the standards in tables 1 and 3. It is noted that the values So of the fluxants 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 various fluxants is the same and has the form:

[00008]$\begin{array}{cc}So=A+B.v_{50}+C.v_{100}+D.CCAI& \left(6\right)\end{array}$ [0161] where:

[0162] A, B, C, D: coefficients determined by statistical processing as described in WO 2021/122349 A1, [0163] V.sub.50: Kinematic viscosity (in mm.sup.2/s) at 50 C., [0164] V.sub.100: Kinematic viscosity (in mm.sup.2/s) at 100 C., [0165] CCAI: Calculated Carbon Aromaticity Index, defined by:

[00009]$\begin{array}{cc}CCAI={}_{15}-81-141.\mathrm{Log}\left[\mathrm{Log}\left(v_{50}+0.85\right)\right]-483.\mathrm{Log}\frac{T+273}{323}& \left(7\right)\end{array}$ [0166] where [0167] P.sub.15: density at 15 C. (in kg/m.sup.3), T: temperature (in C.).

TABLE-US-00001 TABLE 1 Characteristics of the residues RVR 1 RVR 2 RSV RAT Product (411-392) (411-445) (411-669) 411-338) Characteristic Unit Standard Analysis Viscosity at 50 C. mm.sup.2/s ISO 3104:2020 4435 8900 2848 219.5 Viscosity at 100 C. mm.sup.2/s ISO 3104:2020 139.9 227.6 118 21.36 Viscosity at 135 C. mm.sup.2/s ISO 3104:2020 35.81 50.64 Density at 15 C. kg/m.sup.3 ISO 12185:1996 995.4 998.2 984.4 951.0 CCAI 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 8.33 7.35 2.29 (January 2020) CCR % m ISO 10370:2014 18.37 19.52 12.58 S-Value S ASTM D7157-18 1.66 2.06 6.42 Sa 0.56 0.62 0.88 So 0.73 0.78 0.77

TABLE-US-00002 TABLE 2 Characteristics of the fluxants GO FAME 0 FAME 1 FAME 2 UCOME Product 411-393 410-321 410-308 410-182 410-241 Characteristic Unit Analysis Viscosity at 50 C. mm.sup.2/s 3.274 3.665 3.424 3.667 3.819 Viscosity at 100 C. mm.sup.2/s 1.482 1.744 1.667 1.743 1.794 Density at 15 C. kg/m.sup.3 857.5 882.0 885.5 882.7 884.9 CCAI 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

TABLE-US-00003 TABLE 3 Base comprising a visbroken residue Mass composition Product (pour point) of the mixtures RVR 1 (non-measurable) 411-392 80 80 FAME 0 (12 C.) 410-321 20 GO (0 C.) 411-393 20 Characteristic Unit Standard Analysis Measured viscosity mm.sup.2/s ISO 3104-2020 234.9 329.2 at 50 C. Calculated V50 399.5 372.8 difference in % vs 70 13 measurement Reproducibility (%) 7.4 7.4 Measured viscosity mm.sup.2/s ISO 3104-2020 28.15 31.61 at 100 C. Calculated V100 35.7 32.6 difference in % vs 27 3 measurement Reproducibility (%) 5 5 Density at 15 C. kg/m.sup.3 ISO 12185: 1996 970.2 965.0 CCAI 836 827 Pour point C. ISO 3016: 2019 18 Measured S-value S ASTM D7157-18 1.77 Sa 0.55 So 0.79 Calculated S-value S 1.50 1.46 Sa 0.56 0.56 So 0.66 0.64

TABLE-US-00004 TABLE 4 RVR Bases + petroleum fluxant Product (pour point) Mass composition of the mixtures RVR 2 (non-measurable) 441-445 90 80 70 60 45 GO (0 C.) 411-393 10 20 30 40 55 Characteristic Unit Analysis Measured viscosity at 50 C. mm.sup.2/s 1743 480.8 164.5 67.54 24.46 Calculated V50 1889 521.9 179.1 73.49 25.13 difference in % vs measurement 8 9 9 9 3 Reproducibility (%) 7.4 7.4 7.4 7.4 7.4 Measured viscosity at 100 C. mm.sup.2/s 85.51 40.76 21.14 12.1 6.133 Calculated V100 89.06 40.70 21.09 12.08 6.07 difference in % vs measurement 4 0 0 0 1 Reproducibility (%) 4 5 6 7 9 Measured density at 15 C. kg/m.sup.3 981.0 966.1 950.9 936.6 916 CCAI 828 825 821 818 814 Pour point C. 3 9 12 15 15 Difference relative to pour point of the 3 9 12 15 15 flux Measured S-value 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 Calculated S-value 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 Difference between measured and 0.03 0.07 0.09 0.13 0.17 calculated S-value Reproducibility of the method for the 0.31 0.31 0.30 0.29 0.27 measured S-value

TABLE-US-00005 TABLE 5 RVR Bases + renewable fluxant Product (pour point) Mass composition of the mixtures RVR 2 90 80 70 60 35 (non-measurable) FAME 0 (12 C.) 10 20 30 40 65 Characteristic Unit Analysis Measured viscosity mm.sup.2/s 1361 347.5 124.2 54.43 13.08 at 50 C. Calculated V50 1982 565.2 198.0 82.15 15.90 difference in % 46 63 59 51 22 vs measurement Reproducibility (%) 7.4 7.4 7.4 7.4 7.4 Measured viscosity mm.sup.2/s 80.13 36.61 19.52 11.62 4.391 at 100 C. Calculated V100 94.24 44.76 23.79 13.87 4.84 difference in % 18 22 22 19 10 vs measurement Reproducibility (%) 4 5 6 7 11 Measured density kg/m.sup.3 984.4 971.6 959.5 947.5 919.6 at 15 C. CCAI 833 833 833 832 830 Pour point U 0 18 30 33 30 Measured S-value 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 Calculated S-value 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 Difference between 0.11 0.45 0.54 0.75 1.07 measured and calculated S-value Reproducibility of 0.33 0.35 0.35 0.36 0.36 the method for the measured S-value

TABLE-US-00006 TABLE 6 Bases containing RSV Product (pour point) Mass composition of the mixtures RSV 411-469 80.0 80.0 70.0 70.0 70.0 (non-measurable) 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. mm.sup.2/s 223.4 269.5 95.11 113.3 98.69 (measured) Calculated V50 297 276 123 112.3 127.1 difference in % 33 2 29 1 29 vs measurement Reproducibility (%) 7.4 7.4 7.4 7.4 7.4 Viscosity at mm.sup.2/s 28.29 30.28 16.69 17.37 16.96 100 C. (measured) Calculated V100 30.6 28.1 17.9 16 18.2 difference in % 8 7 7 8 7 vs measurement Reproducibility (%) 5 5 6 6 6 Density at 15 C. kg/m.sup.3 961.9 956.6 951.4 943.1 952.1 CCAI 829 821 829 818 829 Pour point C. 24 3 24 9 9 Measured S-value 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 Calculated S-value 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 Difference between 0.09 0.76 0.08 0.37 0.58 measured and calculated S-value Reproducibility of 0.70 0.61 0.67 0.61 0.72 the method for the measured S-value

TABLE-US-00007 TABLE 7 Bases containing RAT Product (pour point) Mass composition of the mixtures RAT (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.sup.2/s 50.09 57.1 29.44 33.34 28.17 29.55 Calculated V50 64.3 60.9 38.6 35.9 36.93 38.54 difference in % vs measurement 28 7 31 8 31 30 Viscosity at 100 C. mm.sup.2/s 9.535 9.814 6.937 7.066 6.759 6.925 (measured) Calculated V100 10.6 10 7.9 7.2 7.703 7.7886 difference in % vs measurement 11 2 14 2 14 12 Density at 15 C. kg/m.sup.3 936.6 931.3 929.4 921.6 930.2 929.3 CCAI Pour point C. 36 33 33 30 33 33 Calculated pour point 33 33 31 31 32 31

[0168] Tables 3 to 7 show differences between the measured and calculated viscosities (at 50 C. and 100 C.) higher for the bases containing FAME or UCOME than the bases containing GO as a fluxant. Moreover, this difference is much higher for the bases containing a visbroken residue than for the bases containing the other residues.

[0169] It should be noted that the reproducibility of the measurement of viscosity is 7.4% at 50 C. The differences in percentage between the measured and calculated viscosities are of this order of magnitude for the bases containing the GO and greater for the bases containing FAME or ECOME, and much greater for the bases containing a visbroken residue relative to the bases containing other types of residues.

[0170] Similarly for the viscosity at 100 C., it is observed that the differences in percentage between the measured and calculated viscosities are less than the reproducibility for the bases containing the GO, greater for the bases containing FAME or ECOME, and much greater for the bases containing a visbroken residue relative to the bases containing other types of residues.

[0171] With regard to the pour point, it is 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 fluxant contained in the base is greater 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 content of fluxant, and is greater for the contents of FAME from 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 fluxant contained in the base greater in absolute value for the RSV bases with FAME or UCOME than for the RSV bases with GO.

[0172] The mixing rule allows to correctly predict the S-value parameters of the RVR/GO bases. However, the measured S-value of the bases with FAME increases with the % of FAME, which should not be the case since the FAMEs are paraffinic compounds. Moreover, the mixing rule predicts a decrease in the S-value. These differences are much greater than the reproducibility of the method and come from the aromaticity So of the matrix: the measurements indeed show than the Sa is constant regardless of the mixture (the Sa of the RVR is not modified since the fluxants do not introduce asphaltenes).

[0173] Good agreement between measured and calculated S-value and So is observed for the RVR/GO bases whereas for the RVR/FAME bases the S-value and the aromaticity So increase while the mixing rule predicts a decrease.

[0174] The examples of tables 4 and 5 with a visbroken residue thus show that the difference between the measured and calculated S-value is less than the reproducibility for the mixtures with GO and much greater for the mixture with FAME (except for the 90% RVR/10% FAME mixture).

[0175] The examples of table 6 show that the difference between the measured and calculated S-value is less than the reproducibility for all the mixtures except for the 80% RSV/20% GO mixture. However, the measured S-value of the mixtures with GO is less than the calculated S-value whereas once again the measured S-value of the mixtures with FAME is greater than the calculated S-value.

[0176] These observations lead to attributing to the FAME a booster effect on the viscosity (reduction), the pour point (reduction) and the stability (increase) of a mixture with a residue. Moreover, this booster effect is more pronounced for the bases containing visbroken residues.

[0177] Table 8 below groups together the properties of fuel mixtures that can be used as marine fuels. A difference between the measured viscosity and the calculated viscosity is observed, the measured viscosity being much lower than the calculated viscosity, even more so for the mixtures containing a visbroken residue.

TABLE-US-00008 TABLE 8 Fuel mixtures Product (pour point) Mass composition of the mixtures RVR 1 411-392 85.0 70.0 60.0 (non-measurable) RSV 70.0 (non-measurable) RAT (36 C.) 70.0 FAME 0 410-321 10.0 20.0 20.0 20.0 20.0 (12 C.) GO (0 C.) 411-393 5.0 10.0 20.0 10.0 10.0 UCOME (3 C.) 410-241 Analysis Unit Viscosity at mm.sup.2/s 428.3 98.92 48.05 98.16 30.53 50 C. (measured) Calculated V50 675.1 149.0 65.0 119 37.7 difference in % 58 51 35 21 23 vs measurement Reproducibility 7.4 7.4 7.4 7.4 (%) Viscosity at mm.sup.2/s 39.91 16.18 10.07 16.33 6.948 100 C. (measured) Calculated V100 48.1 19.3 11.5 17.2 7.7 difference in % 21 19 14 5 11 vs measurement Reproducibility 5 6 7 6 (%) Density at 15 C. kg/m.sup.3 974.8 955.6 941.6 948 926.7 CCAI 835 832 828 825 Pour point C. 12 21 15 18 30 Measured S 1.70 1.73 1.62 5.78 S-value Sa 0.56 0.55 0.55 0.85 So 0.75 0.78 0.73 0.86 Calculated S 1.53 1.40 1.30 4.73 S-value Sa 0.56 0.56 0.56 0.88 So 0.67 0.62 0.57 0.57 Difference 0.17 0.23 0.32 1.05 between measured and calculated S-value

[0178] Comparative example 1: mixture of a vacuum residue and a hydrogenated vegetable oil

[0179] A mixture comprising 70% m/m of a vacuum residue and 30% m/m of a hydrogenated vegetable oil.

[0180] The measured and calculated viscosities of the mixture are presented in table 9. It is observed that the addition of hydrogenated vegetable oils to a residue does not have the booster effect observed with the addition of a FAME.

TABLE-US-00009 TABLE 9 Analysis Unit Viscosity at 50 C. (measured) mm.sup.2/s 71.15 Calculated V50 74.69 difference in % vs measurement 5%

[0181] Comparative example 2: mixture of a shale oil residue and a biodiesel

[0182] Tables 7 and 8 of the document U.S. Pat. No. 10,899,983B1 were reproduced and completed with the calculated viscosities according to the invention and the differences between the measurements. The results are grouped together in tables 10 and 11. The density, the sulfur content and the MCR were calculated in order to verify that the proportions used for the calculations of viscosity were correct.

[0183] With regard to the 35% LCO, 60% VRFO3 mixture, the calculations were carried out with 65% VRFO3, which is consistent with the calculated density, sulfur content and MCR.

[0184] The calculated viscosities and the differences between the calculated and measured viscosities show that the booster effect is not observed with a biodiesel when the residue is a residue coming from shale oil.

TABLE-US-00010 TABLE 10 Completed table 7 of U.S. Pat. No. 10899983B1 35% LCO, 55% LCO, 60% [65%] 35% Gas Oil, 75% Gas 45% VRFO1, VRFO3, 65% VRFO2, Oil, 25% ISO8217 VLSFO, high VLSFO, low ECA, low VRFO5, ECA, RMD80 Spec ratio ratio ratio high ratio Density at 15 C. (kg/m3) <990 901.8 936.9 877.1 870.3 Calculated density 901.5 936.7 877 869.5 Kine. viscosity at 50 C. (cSt) <80 28 202 112 11.6 Calculated kine. viscosity at 50 C. 27 197 111 11.5 difference in % vs measurement 2.2% 2.5% 1.2% 0.8% Sulfur content (% m) <0.50 0.4808 0.4950 0.0403 0.0593 Calculated sulfur content 0.47 0.495 0 0.059 CCAI <860 798 805 752 784 BMCI 42 54 25 31 TE 6 4 0 0 Insoluble N-Heptane (% m) 0.15 0.16 0.15 0.02 MCR (% m) <14 0.18 4.58 0.34 0.74 Calculated MCR 0.21 4.55 0.33 0.71 Pour point ( C.) <30 21 24 29 14

TABLE-US-00011 TABLE 11 Completed table 8 of U.S. Pat. No. 10899983B1 25% 50% 30% 70% Biodiesel, Biodiesel, Biodiesel, Biodiesel, 75% VRFO5, 50% VRFO1, 70% VRFO3, 30% VRFO3, ISO8217 ECA, low ECA, high VLSFO, low VLSFO, low RMD80 Spec ratio ratio ratio ratio Density at 15 C. (kg/m3) <990 907.0 880.9 926.9 0.8999 Calculated density 906.7 880.8 926 898.8 Kine. viscosity at 50 C. (cSt) <80 366 33.0 298 13.8 Calculated kine. viscosity at 50 C. 362 32.62 295 13.6 difference in % vs measurement 1.1% 1.2% 1.0% 1.4% Sulfur content (% m) <0.50 0.0592 0.0148 0.2269 0.1004 Calculated sulfur content 0.0586 0.0148 0.2220 0.0955 CCAI <860 768 774 790 810 BMCI 46 50 59 71 TE 0 0 0 0 Insoluble 0.05 0.11 0.14 0.06 N-Heptane (% m) MCR (% m) <14 2.14 0.11 4.93 2.18 Calculated MCR 2.12 0.11 4.82 2.07 Pour point ( C.) <30 29 27 28 15