EP4183856A1 - Basis für schiffstreibstoff mit einer komponente aus erneuerbarem ursprung und herstellungsverfahren - Google Patents

Basis für schiffstreibstoff mit einer komponente aus erneuerbarem ursprung und herstellungsverfahren Download PDF

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Publication number
EP4183856A1
EP4183856A1 EP21306632.7A EP21306632A EP4183856A1 EP 4183856 A1 EP4183856 A1 EP 4183856A1 EP 21306632 A EP21306632 A EP 21306632A EP 4183856 A1 EP4183856 A1 EP 4183856A1
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EP
European Patent Office
Prior art keywords
component
residue
viscosity
blend
calculated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP21306632.7A
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English (en)
French (fr)
Inventor
Barbara HEYBERGER
Alix BOURDASSOL
Anthony LE ROUX
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TotalEnergies Onetech SAS
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TotalEnergies Onetech SAS
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Publication date
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Priority to EP21306632.7A priority Critical patent/EP4183856A1/de
Priority to PCT/EP2022/082551 priority patent/WO2023094301A1/fr
Publication of EP4183856A1 publication Critical patent/EP4183856A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

Definitions

  • 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).
  • 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).
  • FAME fatty acids of plant or animal origin
  • 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.
  • producers are seeking to integrate more and more components of renewable origin in their manufacture.
  • 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.
  • a hydrocarbon residue component selected from atmospheric residue and vacuum residue from vacuum distillation of atmospheric residue
  • the methyl esters must be added to the hydrocarbon residue component before any other component.
  • 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.
  • 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”.
  • S-1 represents the stability reserve (the higher this reserve, the less the product will be subject to precipitation or compatibility problems).
  • 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).
  • 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.
  • these fatty acid alkyl esters can be used to make a mixture which can form a marine fuel base or a marine fuel.
  • 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).
  • 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.
  • the reduction in viscosity obtained by adding the first component is a definite advantage, since the temperatures of use can be significantly reduced.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the alcohol can be chosen from methanol, ethanol , propanol and mixtures thereof, preferably from methanol, ethanol, and mixtures thereof.
  • 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.
  • 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.
  • the second component is at least one hydrocarbon residue selected from vacuum residue and visbreaking residue.
  • the at least one hydrocarbon residue of the second component is a visbreaking residue.
  • the second component is therefore exclusively of petroleum origin.
  • the second component may consist of at least one hydrocarbon residue, in particular as previously described.
  • 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.
  • 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.
  • 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 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.
  • the two components can be preheated, for example to a temperature lowering the viscosity of the second component.
  • a temperature lowering the viscosity of the second component A person skilled in the art will be able to determine an appropriate preheating temperature.
  • the base according to the invention can be used as a base for manufacturing marine fuel.
  • 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.
  • the base according to the invention is typically mixed with a flux of petroleum origin.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • Table 8 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

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)
EP21306632.7A 2021-11-23 2021-11-23 Basis für schiffstreibstoff mit einer komponente aus erneuerbarem ursprung und herstellungsverfahren Withdrawn EP4183856A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP21306632.7A EP4183856A1 (de) 2021-11-23 2021-11-23 Basis für schiffstreibstoff mit einer komponente aus erneuerbarem ursprung und herstellungsverfahren
PCT/EP2022/082551 WO2023094301A1 (fr) 2021-11-23 2022-11-21 Base pour combustible marin comprenant un composant d'origine renouvelable et methode de fabrication

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EP21306632.7A EP4183856A1 (de) 2021-11-23 2021-11-23 Basis für schiffstreibstoff mit einer komponente aus erneuerbarem ursprung und herstellungsverfahren

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EP4183856A1 true EP4183856A1 (de) 2023-05-24

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2894588A1 (fr) * 2005-12-14 2007-06-15 Total France Sa Liant bitumineux fluxe, fluxant utilise, prepartion et application de ces produits
JP2010111720A (ja) * 2008-11-04 2010-05-20 Osamu Ogata バイオアスファルトおよびその製造方法、並びにバイオアスファルトを用いた重質油の改質方法および石炭の液化方法
WO2018178402A2 (de) * 2017-03-31 2018-10-04 Oiliq Intelligent Solutions Gmbh Zusammensetzung zur verringerung der viskosität von erdöl und erdölrückständen sowie zum lösen und trennen von erdöl und/oder erdölrückständen von anderen flüssigen und/oder festen stoffen
WO2020109653A1 (en) 2018-11-28 2020-06-04 Neste Oyj Marine fuel blend
US10899983B1 (en) * 2020-05-22 2021-01-26 Exxonmobil Research And Engineering Company High napthenic content marine fuel compositions
WO2021018895A1 (en) 2019-07-30 2021-02-04 Shell Internationale Research Maatschappij B.V. Fuel compositions with enhanced stability and methods of making same
WO2021122349A1 (fr) 2019-12-18 2021-06-24 Total Raffinage Chimie Méthode d'estimation du pouvoir solvant so d'un fluxant et méthode de prédiction de la stabilité d'un mélange de flux hydrocarboné(s) contenant des asphaltènes et au moins un fluxant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2894588A1 (fr) * 2005-12-14 2007-06-15 Total France Sa Liant bitumineux fluxe, fluxant utilise, prepartion et application de ces produits
JP2010111720A (ja) * 2008-11-04 2010-05-20 Osamu Ogata バイオアスファルトおよびその製造方法、並びにバイオアスファルトを用いた重質油の改質方法および石炭の液化方法
WO2018178402A2 (de) * 2017-03-31 2018-10-04 Oiliq Intelligent Solutions Gmbh Zusammensetzung zur verringerung der viskosität von erdöl und erdölrückständen sowie zum lösen und trennen von erdöl und/oder erdölrückständen von anderen flüssigen und/oder festen stoffen
WO2020109653A1 (en) 2018-11-28 2020-06-04 Neste Oyj Marine fuel blend
WO2021018895A1 (en) 2019-07-30 2021-02-04 Shell Internationale Research Maatschappij B.V. Fuel compositions with enhanced stability and methods of making same
WO2021122349A1 (fr) 2019-12-18 2021-06-24 Total Raffinage Chimie Méthode d'estimation du pouvoir solvant so d'un fluxant et méthode de prédiction de la stabilité d'un mélange de flux hydrocarboné(s) contenant des asphaltènes et au moins un fluxant
US10899983B1 (en) * 2020-05-22 2021-01-26 Exxonmobil Research And Engineering Company High napthenic content marine fuel compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAPLES, R.E.: "Petroleum Refinery Process Economics", PENNWELL, 2000, ISBN: 978-0-87814-779-3

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