WO2017216171A1 - Mixture for supplying a boiler or a diesel engine, comprising diesel fuel or heating oil and esters and alkanes from the transformation of biomass - Google Patents

Mixture for supplying a boiler or a diesel engine, comprising diesel fuel or heating oil and esters and alkanes from the transformation of biomass Download PDF

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Publication number
WO2017216171A1
WO2017216171A1 PCT/EP2017/064432 EP2017064432W WO2017216171A1 WO 2017216171 A1 WO2017216171 A1 WO 2017216171A1 EP 2017064432 W EP2017064432 W EP 2017064432W WO 2017216171 A1 WO2017216171 A1 WO 2017216171A1
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WO
WIPO (PCT)
Prior art keywords
mixture
carbon atoms
boiler
diesel engine
fuel
Prior art date
Application number
PCT/EP2017/064432
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French (fr)
Inventor
Jean-Yves DUPRE
Jean-Louis REVEL
Original Assignee
Bio-Think
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Publication date
Application filed by Bio-Think filed Critical Bio-Think
Priority to BR112018075781-0A priority Critical patent/BR112018075781A2/en
Priority to CA3027314A priority patent/CA3027314A1/en
Priority to CN201780037001.5A priority patent/CN109642171B/en
Priority to US16/309,555 priority patent/US20190309232A1/en
Priority to EP17734253.2A priority patent/EP3469045A1/en
Publication of WO2017216171A1 publication Critical patent/WO2017216171A1/en

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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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0492—Fischer-Tropsch products
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency

Definitions

  • the present invention relates to a mixture based on liquid fuel for a boiler or diesel engine fuel, comprising particular compounds which make it possible to reduce the emissions of particles and nitrogen oxide from boilers and diesel engines during their operation.
  • Diesel engines are efficient engines from the point of view of the fight against the greenhouse effect since, at equivalent power, they emit about 20% less greenhouse gas emissions than gasoline engines. Nevertheless, they are more and more criticized because of certain emissions harmful for the man, in particular the emissions of particles and oxides of nitrogen. In some large cities, or even entire regions, air pollution from these emissions is a major problem.
  • Particulate and nitrous oxide emissions from diesel engines are regulated in many countries. This is particularly the case in Europe where the limits set by the regulations are more and more stringent (today Euro6 standards). This is also the case in other large countries, particularly the United States, but with very low limits in some states such as those set by the California Air Resources Board.
  • Particles are the subject of two categories of measures:
  • the particles are of different sizes.
  • Four categories of fine particles are generally distinguished: PMio with a diameter of less than 10 ⁇ , PM2.5 with a diameter of less than 2.5 ⁇ , ultrafine particles with a diameter of less than 0.1 ⁇ and nanoparticles, characterized by a diameter less than 50 nm.
  • Diesel engines have made remarkable progress over the last 30 years thanks to the improvement of fuel quality (reduction of sulfur content), combustion (optimization of injection systems) and exhaust gas treatment processes (exhaust gas recirculation, catalytic oxidation systems and particulate filters). But despite a reduction of about 98% in the order of thirty years of particulate emissions on new engines, the problem of particles remains considered serious enough that some cities come to want to ban Diesel vehicles in the city. This is due in particular to the fact that Diesel vehicles are kept for many years (8 to 10 years for private vehicles and often more than 15 years for coaches and trucks).
  • the objective of the present invention is to respond to these problems and in particular to provide an effective, simple and economical solution for reducing emissions from diesel engines and liquid fuel boilers.
  • the invention proposes to incorporate in the diesel engine fuel or in the boiler fuel, together one or more esters and one or more specific alkanes, in addition to those that could already be present in the fuel or fuel .
  • biofuels particularly alkanes from biomass
  • vegetable oils or hydrotreated animal fats treated with hydrogen to remove oxygen atoms
  • carbon or products of the type BTL Biomass to Liquid
  • Other solutions are developed, still experimental, such as hydrotreated pyrolysis oils and alkanes that can be obtained by anaerobic fermentation of biomass followed by Kolbe electrolysis (patent application WO2014170603).
  • hydrocarbons are interesting because they generally have a high cetane number which favors a reduction of NOx emissions. Their effect on particles, however, remains limited.
  • esters from the anaerobic fermentation of biomass in gasoline, gas oil or kerosene (patent FR 2757539A1, Duley-Kaplan, use of esters as fuels or fuels).
  • the present invention is specifically aimed at incorporating into fuels for diesel engines or liquid fuels for a boiler chosen from diesel and heating oil:
  • At least one biosourced ester with a chain length of between 8 and 14 carbon atoms at least one biosourced ester with a chain length of between 8 and 14 carbon atoms
  • ester (s) having a chain length of between 8 and 14 carbon atoms incorporated in the fuel or fuel representing between 1% and 80% by volume of said mixture and the alkane or alkanes of chain length included between 8 and 14 carbon atoms incorporated in the fuel or fuel representing between 1 and 80% by volume of said mixture.
  • biosourced within the meaning of the invention means products derived from biomass, ie agricultural or forestry plants or organic waste.
  • biosourced esters and alkanes can be distinguished from petroleum-based esters and alkanes present in a mixture thanks to a dating that relies on the mass spectrometer measurement of the C14 isotope proportion on the whole. carbon of the molecule.
  • Fossil products have a lower C14 content than products resulting from more recent photosynthesis.
  • esters will reduce the emissions of particles, it is important according to the invention to add alkanes of chain length of between 8 and 14 carbon atoms in addition to those already present in the fuel or fuel, because this avoids an increase in the emission of nitrogen oxide.
  • the mixture according to the invention is a liquid mixture which has a variable composition.
  • a mixture makes it possible to reduce particulate emissions and nitrogen oxide emissions during operation of boilers or diesel engines, without any degradation of other emissions (nitrogen monoxide CO, HC unburned hydrocarbons, etc.).
  • the invention makes it possible to ensure that the mixture meets all specifications of fuels and liquid fuels, including those that are the most difficult to meet, namely the flash point must be above 55 ° C and the calculated cetane number which must be greater than 46.
  • the mixture according to the invention makes it possible to retain the characteristics of the fuel for a diesel engine and of the liquid fuel for a boiler, such as, for example, the cold strength, the viscosity etc.
  • esters and / or alkanes used can in particular be biobased, that is to say be biofuels from agricultural or forestry biomass or organic waste, which then also has an advantage in combating the effect of tight.
  • the invention therefore relates to a mixture for supplying a boiler or a diesel engine, comprising:
  • the ester (s) of chain length of between 8 and 14 carbon atoms incorporated in the mixture may be chosen from all esters of this size. It may be preferentially ethyl hexanoate (C8), butyl butyrate (C8), butyl valerate (C9), butyl hexanoate (C12) and / or butyl caprylate (C14). Preferentially, it is not a question of esters of higher fatty alcohols, that is to say alcohols obtained from the fatty acids of vegetable oils which have been reduced for example by hydrogenation and associated with a short acid such as formic acid or acetic acid.
  • the alkane (s) with a chain length of between 8 and 14 carbon atoms incorporated in the mixture may be chosen from any alkane of this size (connected or unconnected). It may be preferentially decane, dodecane and tetradecane.
  • the specifically selected esters having a chain length of between 8 and 14 carbon atoms advantageously make it possible to continue to comply with all current specifications for diesel fuels and boiler fuels, including at a rate of incorporation. between 1 and 8%, except the maximum level of esters since the esters thus produced are not methyl esters of fatty acids complying with the standard EN14214.
  • the invention is a mixture as described above wherein the ester (s) chain length of between 8 and 14 carbon atoms represent between 1% and 8% by volume of said mixture. This mixture can be distributed as an unmarked fuel in all dispensing pumps.
  • esters used according to the invention can also be used at higher levels.
  • the invention relates to a mixture as described above in which the ester (s) of chain length of between 8 and 14 carbon atoms incorporated represent between 8% and 80% by volume of said mixture which will be distributed either as an unmarked fuel if it is approved for this purpose or as a fuel for captive transport fleets.
  • the ester (s) with a chain length of between 8 and 14 carbon atoms present in the mixture are esters of biobased origin obtained from volatile fatty acids resulting from the anaerobic fermentation of biomass, and esterification with an alcohol.
  • alkane or alkanes of chain length of between 8 and 14 incorporated carbon atoms present in the mixture are alkanes obtained by electrolysis of Kolbe volatile fatty acids resulting from the anaerobic fermentation of the biomass as described in application WO2014170603 or from biomass by gasification and Fischer Tropsch synthesis.
  • the mixture according to the invention in addition to the fuel or fuel, esters and alkanes of specific chain lengths, may optionally contain at least one additional additive to improve the cetane number and / or enhance the reduction of particulate emissions. and / or reduce the emissions of nitrogen oxides by the boiler or the diesel engine during its operation. It may be for example tetranitromethane. Other additives may be added to enhance other functionality of the mixture such as cold strength, viscosity, etc.
  • the mixture according to the invention can be obtained by conventional techniques of the art. Preferably, it is obtained by simply mixing the constituents in the same tank or by mixing two streams in the same pipe. In most countries such a mixture will have to be under the control of the Customs Service.
  • the invention is specifically directed to a method for manufacturing a mixture according to the invention as described above, which consists of incorporating into at least one liquid fuel for a boiler or a diesel engine fuel chosen from diesel fuel or domestic fuel oil:
  • ester (s) of chain length of between 8 and 14 carbon atoms incorporated represent between 1% and 80% by volume of said mixture and in that the alkane or alkanes of chain length between 8 and 14 carbon atoms incorporated represent between 1 and 80% by volume of said mixture.
  • the mixture is produced at a temperature of between 10 and 50 ° C. in a stirred tank or in an apparatus in which the various components mix by crossing the streams.
  • the mixture according to the invention allows a very significant reduction of particulate emissions without there being any degradation.
  • other emissions in particular nitrogen oxide and other emissions such as CO, HC, etc.
  • the rate of reduction of the particles in mass and in number is of the order of double the rate of incorporation (30 to 40% for 20% 60 to 80% incorporation for 40% incorporation, 80 to 90% for 50% incorporation), which is a considerable asset for reducing particulate emissions in cities.
  • the reduction being parallel for the mass and the number of particles, this process does not favor the finest particles which are the most dangerous.
  • the invention therefore specifically relates to the use for supplying a boiler or a diesel engine, of a mixture comprising:
  • ester (s) with a chain length of between 8 and 14 carbon atoms incorporated representing between 1% and 80% by volume of said mixture and the alkane (s) with a chain length of between 8 and 14 carbon atoms; incorporated carbon (s) representing between 1 and 80% by volume of said mixture.
  • the invention aims to use the mixture in a boiler or a diesel engine to reduce particulate emissions and / or reduce nitrogen oxide emissions during operation.
  • the invention also makes it possible to improve the cetane number of the fuel.
  • the mixture according to the invention can be used in any liquid fuel boiler and in any diesel engine, in particular in a fixed diesel engine or a diesel engine installed on transport vehicles or boats or construction machinery or agricultural machinery. or small household gear such as lawn mowers or tillers.
  • At least one additive may be added in the boiler and / or the engine, an additive capable of improving the cetane number and / or enhancing the reduction of particulate emissions and / or reducing the emissions of nitrogen oxides by the boiler or the diesel engine during its operation, and / or at least one additive capable of improving other functionality of the mixture such as cold resistance, viscosity, etc.
  • composition of the various mixtures tested is described in the table (Examples 1 to 5 with different loading rates which represent the number of revolutions per minute of the engine compared to the nominal number of revolutions). These mixtures are obtained by simply mixing the components in cans with manual stirring.
  • the measurements are carried out at the exhaust by a Horiba 9100 (CO, C02, 02, HC and NOx) berry and a PPS PEGASOR particle analyzer on a Renault brand car engine.

Abstract

The subject matter of the invention is a mixture of liquid fuels for boilers or fuels for diesel engines with esters and alkanes, both derived from biomass and having chain lengths of between 8 and 14 carbon atoms, and the use thereof to reduce particle and nitrogen oxide emissions while the boilers or diesel engines are in operation.

Description

MELANGE DESTINE A ALIMENTER UNE CHAUDIERE OU UN MOTEUR DIESEL COMPRENANT DU GAZOLE OU DU FIOUL DOMESTIQUE AINSI QUE DES ESTERS ET DES ALCANES PROVENANT DE LA TRANSFORMATION DE MIXTURE FOR SUPPLYING A BOILER OR A DIESEL ENGINE COMPRISING GASOLINE OR DOMESTIC FUEL AS WELL AS ESTERS AND ALKANES FROM PROCESSING
LA BIOMASSE THE BIOMASS
La présente invention concerne un mélange à base de combustible liquide pour chaudière ou de carburant pour moteur Diesel, comprenant des composés particuliers qui permettent de réduire les émissions de particules et d'oxyde d'azote des chaudières et des moteurs Diesel lors de leur fonctionnement. The present invention relates to a mixture based on liquid fuel for a boiler or diesel engine fuel, comprising particular compounds which make it possible to reduce the emissions of particles and nitrogen oxide from boilers and diesel engines during their operation.
Les moteurs Diesel sont des moteurs performants du point de vue de la lutte contre l'effet de serre puisque, à puissance équivalente, ils émettent environ 20% de gaz à effet de serre de moins que les moteurs à essence. Néanmoins, ils sont de plus en plus critiqués à cause de certaines émissions nocives pour l'homme, en particulier les émissions de particules et d'oxydes d'azote. Dans certaines grandes agglomérations, voire certaines régions entières, la pollution de l'air par ces émissions constitue un problème majeur. Diesel engines are efficient engines from the point of view of the fight against the greenhouse effect since, at equivalent power, they emit about 20% less greenhouse gas emissions than gasoline engines. Nevertheless, they are more and more criticized because of certain emissions harmful for the man, in particular the emissions of particles and oxides of nitrogen. In some large cities, or even entire regions, air pollution from these emissions is a major problem.
Les émissions de particules et d'oxyde d'azote des moteurs Diesel sont dans de nombreux pays réglementées. C'est le cas notamment en Europe où les limites fixées par les réglementations sont de plus en plus strictes (aujourd'hui normes Euro6). C'est le cas aussi dans d'autres grands pays, en particulier aux Etats Unis, mais avec des limites très basses dans certains Etats telles que celles fixées par le California Air Resources Board.  Particulate and nitrous oxide emissions from diesel engines are regulated in many countries. This is particularly the case in Europe where the limits set by the regulations are more and more stringent (today Euro6 standards). This is also the case in other large countries, particularly the United States, but with very low limits in some states such as those set by the California Air Resources Board.
Les particules font l'objet de deux catégories de mesures : Particles are the subject of two categories of measures:
• des mesures qui caractérisent la couleur des gaz d'échappement (mesures de fumées)  • measures that characterize the color of the exhaust gases (smoke measurements)
• des mesures de poids, de diamètre et de nombre de particules.  • measurements of weight, diameter and number of particles.
Les particules sont de différentes tailles. On distingue généralement quatre catégories de particules fines : les PMio d'un diamètre inférieur à 10 μιη, les PM2,5 d'un diamètre inférieur à 2.5 μιη, les particules ultrafines d'un diamètre inférieur à 0.1 μιη et les nanoparticules, caractérisées par un diamètre inférieur à 50 nm. The particles are of different sizes. Four categories of fine particles are generally distinguished: PMio with a diameter of less than 10 μιη, PM2.5 with a diameter of less than 2.5 μιη, ultrafine particles with a diameter of less than 0.1 μιη and nanoparticles, characterized by a diameter less than 50 nm.
La plupart des particules émises par les moteurs Diesel ont un diamètre de moins 1 μιη. Elles représentent donc un mélange de particules fines ou ultrafines et de nanoparticules. Les plus petites sont considérées comme les plus dangereuses pour l'homme.  Most of the particles emitted by diesel engines have a diameter of minus 1 μιη. They therefore represent a mixture of fine or ultrafine particles and nanoparticles. The smaller ones are considered the most dangerous for the man.
Les moteurs Diesel ont fait depuis 30 ans des progrès remarquables grâce à l'amélioration de la qualité des carburants (réduction de la teneur en soufre), à celle du procédé de combustion (optimisation des systèmes d'injection) et à des procédés de traitement des gaz d'échappement (recirculation des gaz d'échappement, systèmes d'oxydation catalytique et filtres à particules). Mais malgré une réduction de l'ordre de 98% depuis une trentaine d'années des émissions de particules sur les moteurs neufs, le problème des particules reste jugé suffisamment sérieux pour que certaines agglomérations en viennent à vouloir bannir les véhicules Diesel en ville. Ceci est dû en particulier au fait que les véhicules Diesel sont conservés un grand nombre d'années (8 à 10 années pour les véhicules des particuliers et souvent plus de 15 ans pour les autocars et les camions). Diesel engines have made remarkable progress over the last 30 years thanks to the improvement of fuel quality (reduction of sulfur content), combustion (optimization of injection systems) and exhaust gas treatment processes (exhaust gas recirculation, catalytic oxidation systems and particulate filters). But despite a reduction of about 98% in the order of thirty years of particulate emissions on new engines, the problem of particles remains considered serious enough that some cities come to want to ban Diesel vehicles in the city. This is due in particular to the fact that Diesel vehicles are kept for many years (8 to 10 years for private vehicles and often more than 15 years for coaches and trucks).
Il serait donc très utile, en complément des mesures de réduction des émissions sur les véhicules neufs et de la promotion des énergies alternatives (véhicules électriques ou véhicules au GNV, par exemple) de trouver des solutions pour les véhicules à moteur Diesel existants.  It would therefore be very useful, in addition to the measures to reduce emissions on new vehicles and the promotion of alternative energies (electric vehicles or NGV vehicles, for example) to find solutions for existing diesel vehicles.
Les mêmes problématiques d'émission de particules et d'oxydes d'azote sont rencontrées avec les combustibles liquides pour chaudières, en particulier avec les vieilles chaudières dont la contribution à la pollution par les particules et les oxydes d'azote est également très significative.  The same problems of particle emission and nitrogen oxides are encountered with liquid fuels for boilers, in particular with old boilers whose contribution to pollution by particles and nitrogen oxides is also very significant.
L'objectif de la présente invention est de répondre à ces problématiques et en particulier de fournir une solution efficace, simple et économique de réduction des émissions des moteurs Diesel et des chaudières à combustible liquide.  The objective of the present invention is to respond to these problems and in particular to provide an effective, simple and economical solution for reducing emissions from diesel engines and liquid fuel boilers.
A cet effet l'invention propose d'incorporer dans le carburant pour moteur Diesel ou dans le combustible pour chaudière, ensemble un ou plusieurs esters et un ou plusieurs alcanes spécifiques, en plus de ceux qui pourraient déjà être présents dans le carburant ou le combustible. For this purpose the invention proposes to incorporate in the diesel engine fuel or in the boiler fuel, together one or more esters and one or more specific alkanes, in addition to those that could already be present in the fuel or fuel .
Avant les années 1990, il n'existait pas de biocarburant pour les moteurs Diesel tandis que l'éthanol était depuis longtemps utilisé dans l'essence, notamment au Brésil et aux USA. Before the 1990s, there was no biofuel for diesel engines while ethanol had long been used in gasoline, especially in Brazil and the USA.
A partir de 1992 a commencé à être développée en France, puis en Europe et dans le monde, l'utilisation du biodiesel qui est un ester méthylique (ou éthylique) d'huile végétale. Aujourd'hui sont utilisés différents types d'esters selon l'origine des matières grasses qui sont transestérifiés par un alcool : huiles végétales, graisses animales ou huiles de friture récupérées. Il s'agit d'esters d'acides gras dont la longueur de chaîne est principalement comprise entre 16 et 18 atomes de carbone. Ces produits sont généralement incorporés à un taux inférieur à 8% dans le gazole banalisé ou bien ils sont utilisés à 20% ou 30% ou exceptionnellement purs dans des flottes captives de transport. Mais les gains que l'on peut attendre en matière de réduction des particules de tels mélanges sont limités (réduction de l'ordre de la moitié du taux d'incorporation des esters). De plus, ces esters ont tendance à augmenter les oxydes d'azote. Ils sont soumis en Europe à la norme EN14214 et, ailleurs dans le monde, à des normes similaires et le taux d'incorporation dans le gazole banalisé est généralement limité à 8% en volume, notamment pour cette raison. From 1992 began to be developed in France, then in Europe and in the world, the use of biodiesel which is a methyl ester (or ethyl) of vegetable oil. Today, different types of esters are used depending on the origin of the fats that are transesterified by an alcohol: vegetable oils, animal fats or recovered cooking oils. These are fatty acid esters whose chain length is mainly between 16 and 18 carbon atoms. These products are generally incorporated at a rate of less than 8% in the normalized diesel or they are used at 20% or 30% or exceptionally pure in captive transport fleets. But the gains that can be expected in reducing the particles of such mixtures are limited (reduction of the order of half the rate of incorporation of the esters). In addition, these esters tend to increase nitrogen oxides. They are submitted in Europe to the EN14214 standard and, in other parts of the world, to similar standards and the rate of incorporation into unconfined diesel is generally limited to 8% by volume, in particular for this reason.
Certains autres biocarburants, en particulier des alcanes venant de la biomasse commencent à être développés, que ce soient les huiles végétales ou graisses animales hydrotraitées (traitées à l'hydrogène pour éliminer les atomes d'oxygène) qui ont elles aussi 16 à 18 atomes de carbone ou bien les produits du type BTL (Biomass to Liquid) issus de la gazéification de la biomasse suivie de la synthèse de Fischer Tropsch. D'autres solutions sont développées, à titre encore expérimental, telles que les huiles de pyrolyse hydrotraitées et des alcanes que l'on peut obtenir par fermentation anaérobie de la biomasse suivie de l'électrolyse de Kolbe (demande de brevet WO2014170603).  Some other biofuels, particularly alkanes from biomass, are beginning to be developed, whether vegetable oils or hydrotreated animal fats (treated with hydrogen to remove oxygen atoms) which also have 16 to 18 carbon atoms. carbon or products of the type BTL (Biomass to Liquid) resulting from the gasification of biomass followed by the synthesis of Fischer Tropsch. Other solutions are developed, still experimental, such as hydrotreated pyrolysis oils and alkanes that can be obtained by anaerobic fermentation of biomass followed by Kolbe electrolysis (patent application WO2014170603).
Ces hydrocarbures sont intéressants parce qu'ils ont en général un indice de cétane élevé qui favorise une réduction des émissions de NOx. Leur effet sur les particules reste cependant limité. These hydrocarbons are interesting because they generally have a high cetane number which favors a reduction of NOx emissions. Their effect on particles, however, remains limited.
Par ailleurs, l'ajout aux carburants de différents composants oxygénés (alcools ou esters) a été proposé depuis de nombreuses années, pour des objectifs qui n'étaient pas la réduction des émissions de particules mais l'amélioration d'autres fonctionnalités (amélioration de la tenue au froid, pouvoir lubrifiant, impact sur l'agriculture, impact sur l'effet de serre,...), par exemple :  In addition, the addition to fuels of various oxygenated components (alcohols or esters) has been proposed for many years, for objectives that were not the reduction of particulate emissions but the improvement of other functionalities (improvement of resistance to cold, lubricity, impact on agriculture, impact on the greenhouse effect, ...), for example:
l'utilisation d'éthanol à plus de 10% dans le gazole mais ceci nécessite la présence d'additifs coûteux  the use of more than 10% ethanol in diesel but this requires the presence of expensive additives
- l'incorporation de butanol dans le gazole (exemple : Energy Conservation and Management Vol 51, Issue 10, October 2010, Effects of butanol-diesel fuel blends on the performance and émissions of a high-speed Dl diesel engine) - the incorporation of butanol in diesel (example: Energy Conservation and Management Vol 51, Issue 10, October 2010, Effects of butanol-diesel fuel blends on the performance and emissions of a high-speed Dl diesel engine)
l'incorporation d'esters provenant de la fermentation anaérobie de la biomasse dans l'essence, le gazole ou le kérosène (brevet FR 2757539A1, Dupré-Kaplan, utilisation d'esters comme carburants ou combustibles).  the incorporation of esters from the anaerobic fermentation of biomass in gasoline, gas oil or kerosene (patent FR 2757539A1, Dupré-Kaplan, use of esters as fuels or fuels).
Des essais ont aussi été réalisés pour l'utilisation d'aldéhydes dans le gazole (Reducing the Emission of Particles from a Diesel Engine by Adding an Oxygenate to the Fuel Environmental Science and Technology 39(16):6260-5 · September 2005) dans le but de réduire les particules émises, mais les émissions d'acétaldéhyde, qui sont elles aussi jugées dangereuses, étaient fortement augmentées. Tests have also been carried out for the use of aldehydes in diesel fuel (Reducing the Emission of Particles from a Diesel Engine by Adding an Oxygenate to the Fuel Environmental Science and Technology 39 (16): 6260-5 · September 2005) in order to reduce emitted particles, but emissions of acetaldehyde, which are also considered to be hazardous, were greatly increased.
Néanmoins, aucune de ces solutions n'a abouti à une solution satisfaisante, qui permet de réduire les émissions de particules et les émissions d'oxyde d'azote lors du fonctionnement des chaudières et des moteurs Diesel.  Nevertheless, none of these solutions has resulted in a satisfactory solution, which reduces particulate emissions and nitrogen oxide emissions during the operation of boilers and diesel engines.
La présente invention vise spécifiquement l'incorporation dans des carburants pour moteur Diesel ou des combustibles liquides pour chaudière choisis parmi le gazole et le fioul domestique :  The present invention is specifically aimed at incorporating into fuels for diesel engines or liquid fuels for a boiler chosen from diesel and heating oil:
- d'au moins un ester biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, et  at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, and
d'au moins un alcane biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone,  at least one biosourced alkane with a chain length of between 8 and 14 carbon atoms,
le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) dans le carburant ou le combustible représentant entre 1% et 80% en volume dudit mélange et le ou les alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) dans le carburant ou le combustible représentant entre 1 et 80% en volume dudit mélange. the ester (s) having a chain length of between 8 and 14 carbon atoms incorporated in the fuel or fuel representing between 1% and 80% by volume of said mixture and the alkane or alkanes of chain length included between 8 and 14 carbon atoms incorporated in the fuel or fuel representing between 1 and 80% by volume of said mixture.
Par biosourcé au sens de l'invention, on entend des produits issus de la biomasse, c'est à dire des plantes agricoles ou forestières ou des déchets organiques.  By biosourced within the meaning of the invention means products derived from biomass, ie agricultural or forestry plants or organic waste.
Il est à noter que les esters et alcanes biosourcés peuvent se distinguer des esters et alcanes d'origine pétrolière présents dans un mélange grâce à une datation qui repose sur la mesure en spectromètre de masse de la proportion de l'isotope C14 sur l'ensemble du carbone de la molécule. Les produits fossiles ont une teneur en C14 plus faible que les produits résultant d'une photosynthèse plus récente.  It should be noted that the biosourced esters and alkanes can be distinguished from petroleum-based esters and alkanes present in a mixture thanks to a dating that relies on the mass spectrometer measurement of the C14 isotope proportion on the whole. carbon of the molecule. Fossil products have a lower C14 content than products resulting from more recent photosynthesis.
Tandis que les esters vont abaisser les émissions de particules, il est important selon l'invention d'ajouter des alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone en plus de ceux déjà présents éventuellement dans le combustible ou le carburant, car cela permet d'éviter une augmentation de l'émission d'oxyde d'azote.  While the esters will reduce the emissions of particles, it is important according to the invention to add alkanes of chain length of between 8 and 14 carbon atoms in addition to those already present in the fuel or fuel, because this avoids an increase in the emission of nitrogen oxide.
Le mélange selon l'invention est un mélange liquide qui présente une composition variable. Avantageusement, un tel mélange permet de réduire les émissions de particules et les émissions d'oxyde d'azote lors du fonctionnement des chaudières ou des moteurs Diesel, sans qu'il y ait une dégradation des autres émissions (monoxydes d'azote CO, hydrocarbures imbrulés HC, etc.). En outre, l'invention permet de faire en sorte que le mélange respecte toutes les spécifications des carburants et combustibles liquides, notamment celles qui sont les plus difficiles à respecter, à savoir le point éclair qui doit être au-dessus de 55°C et l'indice de cétane calculé qui doit être supérieur à 46. De plus, le mélange selon l'invention permet de conserver les caractéristiques du carburant pour moteur Diesel et du combustible liquide pour chaudière, telles que par exemple la tenue à froid, la viscosité, etc. The mixture according to the invention is a liquid mixture which has a variable composition. Advantageously, such a mixture makes it possible to reduce particulate emissions and nitrogen oxide emissions during operation of boilers or diesel engines, without any degradation of other emissions (nitrogen monoxide CO, HC unburned hydrocarbons, etc.). In addition, the invention makes it possible to ensure that the mixture meets all specifications of fuels and liquid fuels, including those that are the most difficult to meet, namely the flash point must be above 55 ° C and the calculated cetane number which must be greater than 46. In addition, the mixture according to the invention makes it possible to retain the characteristics of the fuel for a diesel engine and of the liquid fuel for a boiler, such as, for example, the cold strength, the viscosity etc.
Les esters et/ou les alcanes utilisés peuvent en particulier être biosourcés, c'est à dire être des biocarburants provenant de la biomasse agricole ou forestière ou des déchets organiques, ce qui présente alors aussi un avantage en matière de lutte contre l'effet de serre. The esters and / or alkanes used can in particular be biobased, that is to say be biofuels from agricultural or forestry biomass or organic waste, which then also has an advantage in combating the effect of tight.
D'autres caractéristiques et avantages ressortiront de la description en détail qui va suivre de l'invention.  Other features and advantages will become apparent from the following detailed description of the invention.
L'invention vise donc un mélange destiné à alimenter une chaudière ou un moteur Diesel, comprenant :  The invention therefore relates to a mixture for supplying a boiler or a diesel engine, comprising:
- au moins un combustible liquide pour chaudière ou un carburant pour moteur Diesel choisi parmi le gazole et le fioul domestique, et  at least one liquid fuel for a boiler or a fuel for a diesel engine chosen from diesel fuel and domestic fuel oil, and
au moins un ester biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, incorporé dans le combustible ou le carburant, et - au moins un alcane biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, incorporé dans le combustible ou le carburant,  at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel or fuel, and - at least one biobased alkane with a chain length of between 8 and 14 carbon atoms, incorporated into the fuel or the fuel,
le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentant entre 1% et 80% en volume dudit mélange, préférentiellement entre 5 et 50%, et le ou les alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentant entre 1 et 80% en volume dudit mélange, préférentiellement entre 5 et 50%. the ester (s) with a chain length of between 8 and 14 carbon atoms incorporated representing between 1% and 80% by volume of said mixture, preferably between 5 and 50%, and the alkane (s) of chain between 8 and 14 carbon atoms incorporated (s) representing between 1 and 80% by volume of said mixture, preferably between 5 and 50%.
Le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés présents dans le mélange peuvent être choisis parmi tous les esters de cette taille. Il peut s'agir préférentiellement de l'éthyl hexanoate (C8), du butyl butyrate (C8), du butyl valérate (C9), du butyl hexanoate (C12) et/ou du butyl caprylate (C14). Préférentiellement il ne s'agit pas d'esters d'alcools gras supérieurs, c'est à dire d'alcools obtenus à partir des acides gras des huiles végétales que l'on a réduits par exemple par hydrogénation et que l'on associe à un acide court tel que l'acide formique ou l'acide acétique. The ester (s) of chain length of between 8 and 14 carbon atoms incorporated in the mixture may be chosen from all esters of this size. It may be preferentially ethyl hexanoate (C8), butyl butyrate (C8), butyl valerate (C9), butyl hexanoate (C12) and / or butyl caprylate (C14). Preferentially, it is not a question of esters of higher fatty alcohols, that is to say alcohols obtained from the fatty acids of vegetable oils which have been reduced for example by hydrogenation and associated with a short acid such as formic acid or acetic acid.
Le ou les alcane(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés présents dans le mélange peuvent être choisis parmi tous les alcanes de cette taille (branchés ou non branchés). Il peut s'agir préférentiellement du décane, du dodécane et du tétradécane.  The alkane (s) with a chain length of between 8 and 14 carbon atoms incorporated in the mixture may be chosen from any alkane of this size (connected or unconnected). It may be preferentially decane, dodecane and tetradecane.
Selon l'invention, les esters spécifiquement sélectionnés de longueur de chaîne comprise entre 8 et 14 atomes de carbone permettent avantageusement de continuer à respecter toutes les spécifications actuelles des carburants pour moteurs Diesel et des combustibles pour chaudière, y compris à un taux d'incorporation compris entre 1 et 8%, sauf le taux maximal en esters puisque les esters ainsi produits ne sont pas des esters méthyliques d'acides gras respectant la norme EN14214. Aussi, selon une variante l'invention vise un mélange tel que décrit précédemment dans lequel le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone représentent entre 1% et 8% en volume dudit mélange. Ce mélange peut être distribué comme un carburant banalisé dans toutes les pompes de distribution.  According to the invention, the specifically selected esters having a chain length of between 8 and 14 carbon atoms advantageously make it possible to continue to comply with all current specifications for diesel fuels and boiler fuels, including at a rate of incorporation. between 1 and 8%, except the maximum level of esters since the esters thus produced are not methyl esters of fatty acids complying with the standard EN14214. Also, according to a variant the invention is a mixture as described above wherein the ester (s) chain length of between 8 and 14 carbon atoms represent between 1% and 8% by volume of said mixture. This mixture can be distributed as an unmarked fuel in all dispensing pumps.
En outre, les esters utilisés selon l'invention, peuvent également être utilisés à des taux plus élevés. Aussi, selon une autre variante l'invention vise un mélange tel que décrit précédemment dans lequel le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés représentent entre 8% et 80% en volume dudit mélange qui sera distribué, soit comme un carburant banalisé s'il est agréé à cette fin, soit comme un carburant pour flottes captives de transport.  In addition, the esters used according to the invention can also be used at higher levels. Also, according to another variant, the invention relates to a mixture as described above in which the ester (s) of chain length of between 8 and 14 carbon atoms incorporated represent between 8% and 80% by volume of said mixture which will be distributed either as an unmarked fuel if it is approved for this purpose or as a fuel for captive transport fleets.
Préférentiellement, le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone présents dans le mélange sont des esters d'origine biosourcée obtenus à partir par d'acides gras volatils issus de la fermentation anaérobie de biomasse, et estérification par un alcool.  Preferably, the ester (s) with a chain length of between 8 and 14 carbon atoms present in the mixture are esters of biobased origin obtained from volatile fatty acids resulting from the anaerobic fermentation of biomass, and esterification with an alcohol.
De même, on préférera un mélange dans lequel le ou les alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés présents dans le mélange sont des alcanes obtenus par électrolyse de Kolbe d'acides gras volatils issus de la fermentation anaérobie de la biomasse tels que décrits dans la demande WO2014170603 ou issus de la biomasse par gazéification et synthèse de Fischer Tropsch. Le mélange selon l'invention, en plus du carburant ou combustible, des esters et des alcanes de longueurs de chaîne spécifiques, peut éventuellement contenir au moins un additif supplémentaire pour améliorer l'indice de cétane et/ou renforcer la réduction des émissions de particules et/ou réduire les émissions d'oxydes d'azote par la chaudière ou le moteur Diesel lors de son fonctionnement. Il peut s'agir par exemple du tétranitrométhane. D'autres additifs peuvent être ajoutés pour améliorer d'autres fonctionnalité du mélange comme la tenue au froid, la viscosité, etc. Similarly, a mixture in which the alkane or alkanes of chain length of between 8 and 14 incorporated carbon atoms present in the mixture are alkanes obtained by electrolysis of Kolbe volatile fatty acids resulting from the anaerobic fermentation of the biomass as described in application WO2014170603 or from biomass by gasification and Fischer Tropsch synthesis. The mixture according to the invention, in addition to the fuel or fuel, esters and alkanes of specific chain lengths, may optionally contain at least one additional additive to improve the cetane number and / or enhance the reduction of particulate emissions. and / or reduce the emissions of nitrogen oxides by the boiler or the diesel engine during its operation. It may be for example tetranitromethane. Other additives may be added to enhance other functionality of the mixture such as cold strength, viscosity, etc.
Le mélange selon l'invention peut être obtenu par des techniques classiques de l'homme du métier. Préférentiellement, il est obtenu par un simple brassage des constituants dans une même cuve ou par le mélange de deux flux dans une même canalisation. Dans la plupart des pays un tel mélange devra se faire sous le contrôle du Service des Douanes.  The mixture according to the invention can be obtained by conventional techniques of the art. Preferably, it is obtained by simply mixing the constituents in the same tank or by mixing two streams in the same pipe. In most countries such a mixture will have to be under the control of the Customs Service.
L'invention vise spécifiquement un procédé de fabrication d'un mélange selon l'invention tel que décrit précédemment, qui consiste à incorporer dans au moins un combustible liquide pour chaudière ou un carburant pour moteur Diesel choisi parmi le gazole ou le fioul domestique : The invention is specifically directed to a method for manufacturing a mixture according to the invention as described above, which consists of incorporating into at least one liquid fuel for a boiler or a diesel engine fuel chosen from diesel fuel or domestic fuel oil:
au moins un ester biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, et  at least one biosourced ester of chain length of between 8 and 14 carbon atoms, and
au moins un alcane biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone,  at least one biosourced alkane having a chain length of between 8 and 14 carbon atoms,
de façon à ce que le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés représentent entre 1% et 80% en volume dudit mélange et en ce que le ou les alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés représentent entre 1 et 80% en volume dudit mélange. so that the ester (s) of chain length of between 8 and 14 carbon atoms incorporated represent between 1% and 80% by volume of said mixture and in that the alkane or alkanes of chain length between 8 and 14 carbon atoms incorporated represent between 1 and 80% by volume of said mixture.
Préférentiellement, le mélange est réalisé à une température comprise entre 10 et 50°C dans une cuve agitée ou dans un appareil où les différents composants se mélangent par croisement de flux.  Preferably, the mixture is produced at a temperature of between 10 and 50 ° C. in a stirred tank or in an apparatus in which the various components mix by crossing the streams.
De manière surprenante et avantageuse, le mélange selon l'invention, incorporant des esters et des alcanes particuliers dans les carburants pour moteur Diesel ou dans les combustibles pour chaudière, permet une réduction très significative des émissions de particules sans qu'il y ait une dégradation des autres émissions en particulier d'oxyde d'azote et d'autres émissions tels que CO, HC, etc. Le taux de réduction des particules en masse et en nombre est de l'ordre du double du taux d'incorporation (30 à 40% pour 20% d'incorporation, 60 à 80% pour 40% d'incorporation, 80 à 90% pour 50% d'incorporation), ce qui constitue un atout considérable pour réduire les émissions de particules dans les villes. La réduction étant parallèle pour la masse et le nombre de particules, ce procédé ne favorise pas les particules les plus fines qui sont les plus dangereuses. Surprisingly and advantageously, the mixture according to the invention, incorporating particular esters and alkanes in fuels for diesel engines or in boiler fuels, allows a very significant reduction of particulate emissions without there being any degradation. other emissions, in particular nitrogen oxide and other emissions such as CO, HC, etc. The rate of reduction of the particles in mass and in number is of the order of double the rate of incorporation (30 to 40% for 20% 60 to 80% incorporation for 40% incorporation, 80 to 90% for 50% incorporation), which is a considerable asset for reducing particulate emissions in cities. The reduction being parallel for the mass and the number of particles, this process does not favor the finest particles which are the most dangerous.
L'invention vise donc spécifiquement l'utilisation pour alimenter une chaudière ou un moteur Diesel, d 'un mélange comprenant : The invention therefore specifically relates to the use for supplying a boiler or a diesel engine, of a mixture comprising:
au moins un combustible liquide pour chaudière ou un carburant pour moteur Diesel choisi parmi le gazole ou le fioul domestique , et  at least one liquid fuel for a boiler or a fuel for a diesel engine chosen from diesel fuel or domestic fuel oil, and
au moins un ester biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, incorporé dans le combustible ou le carburant, et au moins un alcane biosourcés de longueur de chaîne comprise entre 8 et 14 atomes de carbone, incorporé dans le combustible ou le carburant,  at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel or fuel, and at least one biobased alkane with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel or fuel,
le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentant entre 1% et 80% en volume dudit mélange et le ou les alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentant entre 1 et 80% en volume dudit mélange. the ester (s) with a chain length of between 8 and 14 carbon atoms incorporated representing between 1% and 80% by volume of said mixture and the alkane (s) with a chain length of between 8 and 14 carbon atoms; incorporated carbon (s) representing between 1 and 80% by volume of said mixture.
En particulier, l'invention vise l'utilisation du mélange dans une chaudière ou un moteur Diesel pour réduire les émissions de particules et/ou réduire les émissions d'oxydes d'azote lors de son fonctionnement. Avantageusement, l'invention permet également d'améliorer l'indice de cétane du carburant.  In particular, the invention aims to use the mixture in a boiler or a diesel engine to reduce particulate emissions and / or reduce nitrogen oxide emissions during operation. Advantageously, the invention also makes it possible to improve the cetane number of the fuel.
Le mélange selon l'invention peut être utilisé dans toute chaudière à combustible liquide et dans tout moteur Diesel, en particulier dans un moteur Diesel fixe ou un moteur Diesel installé sur des véhicules de transport ou des bateaux ou des engins de chantier ou des engins agricoles ou de petits engins domestiques tels que des tondeuses ou des motoculteurs.  The mixture according to the invention can be used in any liquid fuel boiler and in any diesel engine, in particular in a fixed diesel engine or a diesel engine installed on transport vehicles or boats or construction machinery or agricultural machinery. or small household gear such as lawn mowers or tillers.
En plus du mélange selon l'invention, au moins un additif peut être ajouté dans la chaudière et/ou le moteur, additif capable d'améliorer l'indice de cétane et/ou renforcer la réduction des émissions de particules et/ou réduire les émissions d'oxydes d'azote par la chaudière ou le moteur Diesel lors de son fonctionnement, et/ou au moins un additif capable d'améliorer d'autres fonctionnalité du mélange comme la tenue au froid, la viscosité, etc. L'invention est à présent illustrée par des exemples de mélanges selon l'invention et des résultats de tests d'émission sur un banc moteur démontrant leur efficacité. In addition to the mixture according to the invention, at least one additive may be added in the boiler and / or the engine, an additive capable of improving the cetane number and / or enhancing the reduction of particulate emissions and / or reducing the emissions of nitrogen oxides by the boiler or the diesel engine during its operation, and / or at least one additive capable of improving other functionality of the mixture such as cold resistance, viscosity, etc. The invention is now illustrated by examples of mixtures according to the invention and emission test results on a motor bench demonstrating their effectiveness.
La composition des différents mélanges testés est décrite dans le tableau (exemples 1 à 5 avec des taux de charge différents qui représentent le nombre de tours par minute du moteur par rapport au nombre de tours nominal). Ces mélanges sont obtenus par simple mélange des composants dans des bidons avec agitation manuelle. The composition of the various mixtures tested is described in the table (Examples 1 to 5 with different loading rates which represent the number of revolutions per minute of the engine compared to the nominal number of revolutions). These mixtures are obtained by simply mixing the components in cans with manual stirring.
Les mesures sont effectuées à l'échappement par une baie Horiba 9100 (CO, C02, 02, HC et NOx) et un analyseur de particules PPS PEGASOR sur un moteur de voiture de marque Renault  The measurements are carried out at the exhaust by a Horiba 9100 (CO, C02, 02, HC and NOx) berry and a PPS PEGASOR particle analyzer on a Renault brand car engine.
Les résultats obtenus sont présentés dans le tableau ci-après :  The results obtained are shown in the table below:
% %
Carburant , mg/m3 N/cm3 Fumées CO NOx charge  Fuel, mg / m3 N / cm3 Smokes CO NOx charge
20 3,9 19000 0,3 700 85 30 34 170000 2.8 810 116 gasoil de référence 40 43 220000 3.9 1600 238  20 3.9 19000 0.3 700 85 30 34 170000 2.8 810 116 Gas oil reference 40 43 220000 3.9 1600 238
45 20 95000 2 830 370 60 1,5 7000 0,4 220 1300 45 20 95000 2 830 370 60 1.5 7000 0.4 220 1300
EXEMPLE 1 INVENTION 20 3,6 18000 0,25 764 63 gasoil+10%decane+20%butyl butyrate 30 13 62000 1,35 540 114 baisse sensible (-31% en nb) des 40 9 42000 0,92 343 331 particules 45 7 32000 0,75 350 575 sans dégradation sensible des NOx gQ EXAMPLE 1 Invention 20 3.6 18000 0.25 764 63 + 10% diesel decane + 20% butyl butyrate 30 13 62000 1.35 540 114 significant decrease (-31% by nb) of 40 9 42000 0.92 343 331 particles 45 7 32000 0.75 350 575 without appreciable degradation of NOx g Q
1,8 8500 0,23 475 1214 1.8 8500 0.23 475 1214
EXEMPLE 2 INVENTION 20 2,3 11000 0,17 800 55 gasoil+20%decane+20%butyl hexanoate 30 15 70000 1,65 575 100 baisse sensible (-48% en nb) des 4Q INVENTION EXAMPLE 2 20 2.3 11000 0.17 800 55 Diesel + 20% + 20% decane butyl hexanoate 30 15 70000 1.65 575 100 significant decrease (-48% by nb) 4Q
19 88000 2,2 920 222 particules  19 88000 2.2 920 222 particles
légère baisse (-15%) des NOx 45 18,5 90000 2,35 880 235 slight decrease (-15%) of NOx 45 18.5 90000 2.35 880 235
60 1,3 6000 0,29 270 1168 60 1.3 6000 0.29 270 1168
20 3,2 15000 0,23 870 4120 3.2 15000 0.23 870 41
EXEMPLE 3 INVENTION 30 15,5 74000 1,6 591 92 gasoil+20%decane+20%butyl butyrate 4Q INVENTION EXAMPLE 3 30 15.5 74000 1.6 591 92 + 20% diesel decane + 20% butyl butyrate 4Q
31 148000 3,5 1806 160 baisse sensible (-36% en nb) des  31 148000 3.5 1806 160 significant decrease (-36% in nb) of
45  45
particules 19 82000 2,12 960 240 légère baisse (-19%) des NOx g0 particles 19 82000 2.12 960 240 slight decrease (-19%) of NOx g0
1,5 6800 0,32 465 1186 1.5 6800 0.32 465 1186
20 0,3 1600 0,03 1240 7220 0.3 1600 0.03 1240 72
EXEMPLE 4 INVENTION 30 3 14000 0,22 530 122 30% gasoil+20% décane+50% butyl 4Q EXAMPLE 4 INVENTION 30 3 14000 0.22 530 122 30% gas oil + 20% decane + 50% butyl 4Q
5 23000 0,34 337 228 butyrate  5 23000 0.34 337 228 butyrate
forte baisse (-88% en nb) des particules 5  strong decrease (-88% in nb) of the particles 5
légère baisse (-11%) des NOx 4,5 21000 0,42 347 300  slight decrease (-11%) of NOx 4.5 21000 0.42 347 300
20 1 5000 0,04 1218 50 20 1 5000 0.04 1218 50
EXEMPLE 5 INVENTION 30 5,5 28000 0,41 550 101 1/3 gasoil + 1/3 décane + 1/3 butyl 4Q INVENTION EXAMPLE 5 30 5.5 28000 0.41 550 101 1/3 diesel + 1/3 + 1/3 decane butyl 4Q
13 62000 1,00 566 182 butyrate  13 62000 1.00 566 182 butyrate
forte baisse (-74% en nb) des particules 45  sharp drop (-74% in nb) of the particles 45
et baisse sensible (-27%) des NOx 7 35000 0,53 380 263 Ces résultats montrent que les alcanes n'ont pas d'impact favorable significatif sur les émissions de particules, tandis que les esters et les alcanes ensemble permettent de manière inattendue des réductions très significatives des particules plus ou moins proportionnelles au taux d'ester (baisse des particules de l'ordre du double du taux d'esters incorporés) en même temps qu'une baisse significative des NOx. L'exemple 5 est à cet égard très démonstratif. and significant decrease (-27%) of NOx 7 35000 0.53 380 263 These results show that alkanes have no significant favorable impact on particle emissions, while esters and alkanes together unexpectedly allow very significant reductions of particles more or less proportional to the ester level (decrease particles of the order of twice the level of incorporated esters) at the same time as a significant decrease of NOx. Example 5 is very demonstrative in this respect.
Les autres paramètres (CO, HC), ne sont pas dégradés. Il y a même une baisse sensible du CO. En ajustant les taux d'esters et d'alcanes, il va ainsi être possible d'optimiser les émissions des moteurs Diesel.  The other parameters (CO, HC) are not degraded. There is even a significant decline in CO. By adjusting the levels of esters and alkanes, it will thus be possible to optimize the emissions of diesel engines.

Claims

REVENDICATIONS
1. Mélange destiné à alimenter une chaudière ou un moteur Diesel, comprenant : 1. Mixture intended to power a boiler or a Diesel engine, comprising:
au moins un combustible liquide pour chaudière ou un carburant pour moteur Diesel choisi parmi le gazole ou le fioul domestique, et at least one liquid fuel for a boiler or a fuel for a diesel engine chosen from diesel or domestic fuel oil, and
au moins un ester biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, incorporé dans le combustible, et at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel, and
au moins un alcane biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, incorporé dans le combustible, at least one biosourced alkane with a chain length of between 8 and 14 carbon atoms, incorporated in the fuel,
le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentant entre 1% et 80% en volume dudit mélange et le ou les alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentant entre 1 et 80% en volume dudit mélange. the ester(s) with a chain length of between 8 and 14 incorporated carbon atoms representing between 1% and 80% by volume of said mixture and the alkane(s) with a chain length of between 8 and 14 atoms of incorporated carbon(s) representing between 1 and 80% by volume of said mixture.
2. Mélange selon la revendication 1, caractérisé en ce que le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentent entre 5% et 50% en volume dudit mélange. 2. Mixture according to claim 1, characterized in that the ester(s) with a chain length of between 8 and 14 incorporated carbon atoms represent between 5% and 50% by volume of said mixture.
3. Mélange selon l'une des précédentes revendications, caractérisé en ce que le ou les alcane(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) représentent entre 5% et et 50 % en volume dudit mélange. 3. Mixture according to one of the preceding claims, characterized in that the alkane(s) with a chain length of between 8 and 14 incorporated carbon atoms represent between 5% and 50% by volume of said mixture. .
4. Mélange selon l'une des précédentes revendications, caractérisé en ce que le ou les alcanes de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) dans le mélange sont des alcanes obtenus par électrolyse de Kolbe d'acides gras volatils issus de la fermentation anaérobie de biomasse ou des alcanes issus de la biomasse par gazéification et synthèse de Fischer-Tropsch. 4. Mixture according to one of the preceding claims, characterized in that the alkane(s) of chain length between 8 and 14 carbon atoms incorporated in the mixture are alkanes obtained by Kolbe electrolysis of fatty acids volatiles from anaerobic fermentation of biomass or alkanes from biomass by gasification and Fischer-Tropsch synthesis.
5. Mélange selon l'une des précédentes revendications, caractérisé en ce que le ou les esters de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporé(s) dans le mélange sont des esters dont la partie acide est obtenue à partir d'acides gras volatils issus de la fermentation anaérobie de la biomasse, et estérification par un alcool. 5. Mixture according to one of the preceding claims, characterized in that the ester(s) of chain length between 8 and 14 carbon atoms incorporated in the mixture are esters whose acid part is obtained from volatile fatty acids resulting from anaerobic fermentation of biomass, and esterification with an alcohol.
6. Mélange selon l'une des précédentes revendications, caractérisé en ce qu'il comprend au moins un additif supplémentaire capable d'améliorer l'indice de cétane et/ou de réduire les émissions de particules et/ou de réduire les émissions d'oxydes d'azote par la chaudière ou le moteur Diesel en fonctionnement. 6. Mixture according to one of the preceding claims, characterized in that it comprises at least one additional additive capable of improving the cetane index and/or to reduce particle emissions and/or reduce nitrogen oxide emissions from the boiler or diesel engine in operation.
7. Mélange selon l'une des précédentes revendications, caractérisé en ce qu'il comprend au moins un additif supplémentaire capable d'améliorer la tenue au froid et/ou la viscosité. 7. Mixture according to one of the preceding claims, characterized in that it comprises at least one additional additive capable of improving cold resistance and/or viscosity.
8. Procédé de fabrication d'un mélange selon l'une des précédentes revendications, caractérisé en ce qu'il consiste à incorporer dans au moins un combustible liquide pour chaudière ou un carburant pour moteur Diesel choisi parmi le gazole ou le fioul domestique : 8. Process for manufacturing a mixture according to one of the preceding claims, characterized in that it consists of incorporating into at least one liquid fuel for a boiler or a fuel for a diesel engine chosen from diesel or domestic fuel oil:
au moins un ester biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, et at least one biosourced ester with a chain length of between 8 and 14 carbon atoms, and
au moins un alcane biosourcé de longueur de chaîne comprise entre 8 et 14 atomes de carbone, at least one biosourced alkane with a chain length of between 8 and 14 carbon atoms,
de façon à ce que le ou les ester(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés représentent entre 1% et 80% en volume dudit mélange et en ce que le ou les alcane(s) de longueur de chaîne comprise entre 8 et 14 atomes de carbone incorporés représentent entre 1 et 80% en volume dudit mélange. so that the ester(s) of chain length between 8 and 14 incorporated carbon atoms represent between 1% and 80% by volume of said mixture and in that the alkane(s) of length of chain of between 8 and 14 incorporated carbon atoms represents between 1 and 80% by volume of said mixture.
9. Utilisation d'un mélange selon l'une des revendications 1 à 7 pour alimenter une chaudière ou un moteur Diesel. 9. Use of a mixture according to one of claims 1 to 7 to power a boiler or a Diesel engine.
10. Utilisation selon la revendication 9 dans une chaudière ou un moteur Diesel pour réduire les émissions de particules lors du fonctionnement de la chaudière ou du moteur. 10. Use according to claim 9 in a boiler or a Diesel engine to reduce particle emissions during operation of the boiler or engine.
11. Utilisation selon la revendication 9 ou 10 dans une chaudière ou un moteur Diesel pour réduire les émissions d'oxydes d'azote lors du fonctionnement de la chaudière ou du moteur. 11. Use according to claim 9 or 10 in a boiler or a Diesel engine to reduce nitrogen oxide emissions during operation of the boiler or engine.
12. Utilisation selon l'une des revendications 9 à 11 dans un moteur Diesel pour améliorer l'indice de cétane du carburant. 12. Use according to one of claims 9 to 11 in a Diesel engine to improve the cetane number of the fuel.
13. Utilisation selon l'une des revendications 9 à 12 dans une chaudière ou un moteur diesel dans lesquels d'autres additifs sont ajoutés pour améliorer l'indice de cétane ou renforcer la réduction des émissions de particules ou d'oxydes d'azote. 13. Use according to one of claims 9 to 12 in a boiler or a diesel engine in which other additives are added to improve the cetane index or reinforce the reduction of particulate or nitrogen oxide emissions.
14. Utilisation selon l'une des revendications 9 à 13 dans un moteur Diesel dans lesquels d'autres additifs sont ajoutés pour améliorer la tenue au froid et/ou la viscosité. 14. Use according to one of claims 9 to 13 in a Diesel engine in which other additives are added to improve cold resistance and/or viscosity.
15. Utilisation selon l'une des revendications 9 à 14 dans un moteur Diesel fixe ou un moteur Diesel installé sur des véhicules de transport ou des bateaux ou des engins de chantier ou des engins agricoles ou de petits engins domestiques. 15. Use according to one of claims 9 to 14 in a stationary Diesel engine or a Diesel engine installed on transport vehicles or boats or construction machinery or agricultural machinery or small domestic machinery.
PCT/EP2017/064432 2016-06-13 2017-06-13 Mixture for supplying a boiler or a diesel engine, comprising diesel fuel or heating oil and esters and alkanes from the transformation of biomass WO2017216171A1 (en)

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BR112018075781-0A BR112018075781A2 (en) 2016-06-13 2017-06-13 mixture for fueling a boiler or diesel engine, process for making a mixture for fueling a boiler or diesel engine and use of a mixture for fueling a boiler or diesel engine
CA3027314A CA3027314A1 (en) 2016-06-13 2017-06-13 Mixture for supplying a boiler or a diesel engine, comprising diesel fuel or heating oil and esters and alkanes from the transformation of biomass
CN201780037001.5A CN109642171B (en) 2016-06-13 2017-06-13 Mixture comprising specific esters and alkanes intended to supply boilers or diesel engines
US16/309,555 US20190309232A1 (en) 2016-06-13 2017-06-13 Mixture for supplying a boiler or a diesel engine, comprising diesel fuel or heating oil and esters and alkanes from the transformation of biomass
EP17734253.2A EP3469045A1 (en) 2016-06-13 2017-06-13 Mixture for supplying a boiler or a diesel engine, comprising diesel fuel or heating oil and esters and alkanes from the transformation of biomass

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FR1655403 2016-06-13
FR1655403A FR3052459B1 (en) 2016-06-13 2016-06-13 MIXTURE FOR SUPPLYING A BOILER OR DIESEL ENGINE COMPRISING PARTICULAR ESTERS AND ALKANES

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