EP2094820A2 - Diesel fuel containing long-chain glycerol acetals - Google Patents

Diesel fuel containing long-chain glycerol acetals

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Publication number
EP2094820A2
EP2094820A2 EP07858572A EP07858572A EP2094820A2 EP 2094820 A2 EP2094820 A2 EP 2094820A2 EP 07858572 A EP07858572 A EP 07858572A EP 07858572 A EP07858572 A EP 07858572A EP 2094820 A2 EP2094820 A2 EP 2094820A2
Authority
EP
European Patent Office
Prior art keywords
glycerol
diesel fuel
carbon atoms
acetals
sub
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Withdrawn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
EP07858572A
Other languages
German (de)
French (fr)
Inventor
Jean-Luc Dubois
Sara Iborra Chornet
Avelino Corma Canos
Alexandra I. Lucienne Velty
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Arkema France SA
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Arkema France SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Consejo Superior de Investigaciones Cientificas CSIC, Universidad Politecnica de Valencia, Arkema France SA filed Critical Consejo Superior de Investigaciones Cientificas CSIC
Publication of EP2094820A2 publication Critical patent/EP2094820A2/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development

Definitions

  • the present invention relates to a diesel fuel composition containing long-chain cyclic glycerol acetals.
  • French Oil also targets diesel fuel compositions containing glycerol acetals and / or glycerol acetal ethers.
  • the Examples of this patent illustrate the use of some of these acetals and glycerol acetal ethers in diesel fuel compositions at 5% content by weight, by measuring the impact on particle emission.
  • the Applicant has unexpectedly discovered, with respect to the prior art, that it is possible to propose glycerol acetals having a cetane number in high mixture, and therefore able to enter substantial proportions in diesel fuel compositions making it possible to 'obtain the environmental benefits, related to the natural origin of the added compounds, and the energy performance compatible with the final application.
  • the present invention relates to a diesel fuel composition containing long chain glycerol acetals.
  • the invention relates to a diesel fuel composition consisting of a diesel fuel base of either petroleum origin or of vegetable origin and from 1 to 60% by weight of glycerol acetals, characterized in that the acetal of glycerol meets the following formula
  • R 1 is an alkyl radical comprising from 5 to 13 carbon atoms of which at least 5 form a linear chain
  • R 2 is either H or an alkyl radical of 1 to 7 carbon atoms, the total number of carbon atoms of R 1 R 2 being less than 20 and preferably less than 12.
  • Preferred compositions of the invention are those in which R 1 is an n-alkyl radical of 6 carbon atoms or an isoalkyl radical of 7 carbon atoms, R2 being These two acetals come from the first of the reaction of glycerol on n-heptanal (also called heptanaldehyde), and the second of glycerol on 2-ethylhexanal. These two aldehydes are preferred because of their availability on the market and the plant origin for the first.
  • the glycerol acetals of the invention are prepared by reaction of an aldehyde or a ketone with glycerol, for example by the methods described in the article by FAJ Meskens titled “Methods for the Preparation of Acetals from Alcohols or Oxiranes”. and Carbonyl Compounds »pages 501 to 522 of the journal” Synthesis "of July 1981 (Georg Thieme Verlag - Stuttgart - New York).
  • the glycerol acetals according to the invention can be prepared according to various other methods: by reactive extraction between the aldehyde and a glycerol solution, the acetal produced then being less soluble in the aqueous phase can be easily extracted and separated; by reaction between the glycerol and the aldehyde simulated moving bed in order to strongly shift the equilibrium of the acetalization reactions.
  • the acetals of the invention must have physical characteristics compatible with standards such as, for example, the French standard NF EN 590. Main characteristics are density, boiling point, flash point, solubility in water and cetane number.
  • the long-chain glycerol acetals are particularly interesting because they have a high cetane number and a high oxygen content (14 to 25% by weight) which promotes the reduction of particulate emissions leading to a reduction of NO x .
  • they can be produced from renewable raw materials, both for glycerol which is a co-product of biodiesel obtained by transesterification of triglycerides, and for heptanaldehyde, which can be obtained by thermal cracking from esterified natural oils. of castor oil.
  • Cetane boosters may be added to typical diesel cuts as used in the present invention, preferably at levels of at most 1% by weight. Cetane boosters may be selected from nitro compounds and dialkyl peroxides.
  • Example 1 Preparation of a mixture between a gas oil and the acetal.
  • the cyclic acetal is prepared by reacting glycerol with heptanaldehyde.
  • An aqueous solution of glycerol (60% by weight of glycerol, 40% by weight of water) containing 10 moles of glycerol (ie 920 g) is mixed with 10 moles of heptanaldehyde (ie 114 g) or a molar ratio of heptanaldehyde / glycerol of 1.
  • a solution of 35% hydrochloric acid is added to the aqueous solution of glycerol + heptanaldehyde in a proportion of 15% relative to glycerol.
  • the mixture is then heated and maintained at 40 ° C. for 5 hours. with stirring.
  • the acetal obtained is then mixed with a diesel fuel base representative of Euro 2000 formulations: density of the order of 0.830 at 15 ° C., sulfur content of about 290 ppm, cetane number of 51, distillation interval 170-360 ° C.
  • the acetal / fuel base ratio is 10% by weight.
  • the cetane number of the mixture is then measured according to the ISO 5165 standard. This is slightly greater than 51, which makes it possible to deduce that the cetane number of the acetal in admixture is of the order of 52. 2 Comparative tests of the mixture with the diesel fuel base.
  • Tests were conducted to evaluate particle emission performance of diesel fuel compositions containing 10% by weight of glycerol and heptanaldehyde acetal compared to those obtained with reference diesel fuel. .
  • the tests were conducted on a diesel vehicle equipped with a direct injection engine. These tests were carried out on the cycle described in European Directive 70/220 / EC, amended by Directive 98/69 / EC (called MVEG-Hs EURO 2000 cycle). This cycle is composed of an urban phase (EUDC cycle with a length of 4,052 km), and an extra-urban phase (ECE cycle with a length of 6,955 km).
  • EUDC cycle urban phase
  • ECE cycle extra-urban phase

Abstract

The invention relates to a diesel fuel composition containing from 1 to 60% by weight of cyclic, long-chain glycerol acetals corresponding to the following formula (I) and/or in which R<SUB>1</SUB> is an alkyl radical containing from 5 to 13 carbon atoms, at least 5 of which form a linear chain, and R<SUB>2 </SUB>is either H or an alkyl radical containing from 1 to 7 carbon atoms, wherein the total number of carbon atoms of R<SUB>1</SUB> + R<SUB>2</SUB> is less than 20, and preferably less than 12.

Description

CARBURANT DIESEL CONTENANT DES ACETALS DE GLYCEROL A DIESEL FUEL CONTAINING ACETALS OF GLYCEROL A
LONGUE CHAINELONG CHAIN
La présente invention a pour objet une composition de carburant diesel contenant des acétals cycliques de glycérol à longue chaîne.The present invention relates to a diesel fuel composition containing long-chain cyclic glycerol acetals.
La maîtrise de l'énergie et les économies qu'elle implique entraînent pour l'industrie automobile mondiale une évolution vers les moteurs économiques type diesel et en outre des moteurs diesel fonctionnant avec des carburants de substitution. Cependant, les inconvénients de ces moteurs diesel sont bien connus notamment en matière de pollution qui est par ailleurs une autre priorité de l'ensemble des gouvernements. Il faut donc disposer de carburants économes du pétrole, permettant de faire fonctionner les moteurs de manière satisfaisante dans une large gamme de conditions d'utilisation en matière de températures, aux normes de pollution actuelles et à leur évolution prévisible notamment en matière d'émissions, en particulier les imbrûlés.Energy management and the savings it entails lead the global automotive industry to shift towards diesel-type economic engines and, in addition, diesel engines powered by alternative fuels. However, the disadvantages of these diesel engines are well known particularly in terms of pollution which is also another priority of all governments. It is therefore necessary to have petroleum-saving fuels that make it possible to operate the engines satisfactorily under a wide range of temperature conditions of use, current pollution standards and their foreseeable evolution, particularly in terms of emissions. especially the unburned.
L'utilisation des acétals de glycérol comme additifs des carburants diesel a déjà fait l'objet d'études.The use of glycerol acetals as diesel fuel additives has already been studied.
L'étude de Richard Wessendorf parue dans « Erdol und Kohle - Erdgas - Petrochemie vereinigt mit Brennstoff-Chemie Bd. 48, Heft 3,Marz 1995, pages 138 à 143, fait un point fort complet sur l'utilisation des divers dérivés du glycérol en tant que constituants d'un combustible. Le quatrième chapitre de cette étude est consacré aux acétals cycliques. Son tableau Xl illustre les performances obtenues avec les acétals de glycérol dans des compositions carburantes pour moteurs diesel. On peut observer à ce sujet que les diverses compositions illustrées - GAC 4 à GAC 10 - donnent des résultats particulièrement décevants en matière d'indice de cétane. En effet, une addition de simplement 10 % poids de ces acétals fait passer le carburant bien en- dessous des normes admissibles pour les carburants diesel en matière d'indice de cétane. La demande de brevet européen 1 321 502, déposée par l'InstitutThe study by Richard Wessendorf published in "Erdol und Kohle - Erdgas - Petrochemie vereinigt mit Brennstoff-Chemie Bd. 48, Heft 3, Marz 1995, pages 138 to 143, makes a complete point on the use of the various derivatives of glycerol as constituents of a fuel. The fourth chapter of this study is devoted to cyclic acetals. His table Xl illustrates the performances obtained with glycerol acetals in fuel compositions for diesel engines. It can be observed in this regard that the various compositions illustrated - GAC 4 to GAC 10 - give particularly disappointing results in terms of cetane number. Indeed, an addition of just 10% by weight of these acetals puts the fuel well below the standards for diesel fuel cetane number. European Patent Application 1,321,502, filed by the Institute
Français du Pétrole, vise aussi des compositions de carburants diesel contenant des acétals de glycérol et/ou des éthers d'acétals de glycérol. Les exemples de ce brevet illustrent l'utilisation de certains de ces acétals et éthers d'acétals de glycérol dans des compositions carburants diesel, et cela à 5 % de teneur en poids, en mesurant l'incidence sur l'émission de particules.French Oil, also targets diesel fuel compositions containing glycerol acetals and / or glycerol acetal ethers. The Examples of this patent illustrate the use of some of these acetals and glycerol acetal ethers in diesel fuel compositions at 5% content by weight, by measuring the impact on particle emission.
Quel que soit l'intérêt scientifique de ces résultats, il est clair qu'ils ne permettent pas d'envisager l'utilisation en quantité substantielle de ces molécules dans des carburants commerciaux en raison de l'incidence de celles- ci sur l'indice de cétane des carburants. En effet, dans l'article de R. Wessendorf, le tableau Xl montre que l'indice de cétane de l'acétal en mélange (avec le carburant diesel de base) le plus élevé n'est que de 25 pour l'acétal de glycérol et butyraldéhyde (GAC 6), et pour l'acétal du glycérol et 2- ethylbutyraldéhyde (GAC 10). Les autres acétals décrits ont des indices de cétane inférieurs à 6. Les données en matière d'indice de cétane pour les acétals décrits par NFP dans sa demande de brevet européen ne sont pas mentionnées. En considérant les similitudes de structures celles-ci ne sont pas différentes de celles figurant dans la publication de R. Wessendorf.Whatever the scientific interest of these results, it is clear that they do not allow to consider the use in substantial quantities of these molecules in commercial fuels because of the impact of these on the index cetane fuels. Indeed, in the article by R. Wessendorf, Table Xl shows that the cetane number of the acetal in admixture (with the basic diesel fuel) is only 25 for the acetal. glycerol and butyraldehyde (GAC 6), and for glycerol acetal and 2-ethylbutyraldehyde (GAC 10). The other acetals described have cetane numbers of less than 6. The cetane number data for the acetals described by NFP in its European patent application are not mentioned. Considering the similarities of structures these are not different from those appearing in R. Wessendorf's publication.
La demanderesse a découvert de manière inattendue par rapport à l'art antérieur qu'il était possible de proposer des acétals de glycérol présentant un indice de cétane en mélange élevé, et donc pouvant entrer dans des proportions substantielles dans les compositions de carburants diesel permettant d'obtenir les avantages en matière d'environnement, liés à l'origine naturelle des composés ajoutés, et les performances énergétiques compatibles avec l'application finale.The Applicant has unexpectedly discovered, with respect to the prior art, that it is possible to propose glycerol acetals having a cetane number in high mixture, and therefore able to enter substantial proportions in diesel fuel compositions making it possible to 'obtain the environmental benefits, related to the natural origin of the added compounds, and the energy performance compatible with the final application.
La présente invention a pour objet une composition de carburant diesel contenant des acétals de glycérol à longue chaîne. L'invention vise une composition de carburant diesel constituée d'une base de carburant diesel soit d'origine pétrolière, soit d'origine végétale et de 1 à 60 % en poids d'acétals de glycérol, caractérisée en ce que l'acétal de glycérol répond à la formule suivanteThe present invention relates to a diesel fuel composition containing long chain glycerol acetals. The invention relates to a diesel fuel composition consisting of a diesel fuel base of either petroleum origin or of vegetable origin and from 1 to 60% by weight of glycerol acetals, characterized in that the acetal of glycerol meets the following formula
et/ou dans laquelle Ri est un radical alkyle comprenant de 5 à 13 atomes de carbone dont 5 au moins forment une chaîne linéaire, R2 est soit H, soit un radical alkyle de 1 à 7 atomes de carbone, le nombre total des atomes de carbone de Ri + R2 étant inférieur à 20 et de préférence inférieur à 12. Les compositions de l'invention préférées sont celles dans lesquelles Ri est un radical n-alkyle de 6 atomes de carbone ou un radical iso-alkyle de 7 atomes de carbone, R2 étant H. Ces deux acétals proviennent, le premier de la réaction du glycérol sur le n-heptanal (appelé aussi heptanaldéhyde), et le second, du glycérol sur le 2-éthylhexanal. Ces deux aldéhydes sont préférés du fait de leur disponibilité sur le marché et de l'origine végétale pour le premier. and or in which R 1 is an alkyl radical comprising from 5 to 13 carbon atoms of which at least 5 form a linear chain, R 2 is either H or an alkyl radical of 1 to 7 carbon atoms, the total number of carbon atoms of R 1 R 2 being less than 20 and preferably less than 12. Preferred compositions of the invention are those in which R 1 is an n-alkyl radical of 6 carbon atoms or an isoalkyl radical of 7 carbon atoms, R2 being These two acetals come from the first of the reaction of glycerol on n-heptanal (also called heptanaldehyde), and the second of glycerol on 2-ethylhexanal. These two aldehydes are preferred because of their availability on the market and the plant origin for the first.
Les acétals de glycérol de l'invention sont préparés par réaction d'un aldéhyde ou d'une cétone sur le glycérol, par exemple selon les procédés décrits dans l'article de F. A. J. Meskens intitulé « Methods for the Préparation of Acétals from Alcools or Oxiranes and Carbonyl Compounds » pages 501 à 522 de la revue « Synthesis » de juillet 1981 (Georg Thieme Verlag - Stuttgart - New York).The glycerol acetals of the invention are prepared by reaction of an aldehyde or a ketone with glycerol, for example by the methods described in the article by FAJ Meskens titled "Methods for the Preparation of Acetals from Alcohols or Oxiranes". and Carbonyl Compounds »pages 501 to 522 of the journal" Synthesis "of July 1981 (Georg Thieme Verlag - Stuttgart - New York).
Pour ce qui concerne la synthèse d'acétals cycliques à longue chaîne, on peut citer l'article de G. Stefanovic et G. Petrovic, Bulletin T Liv. de l'Académie Serbe des Sciences et des arts, 54(14) (1976) 53-73, qui décrit la synthèse de plusieurs acétals de glycérol à longue chaîne dont l'heptilidène glycérol (réaction avec l'heptanaldéhyde), l'octilidène glycérol (réaction avec l'octanaldéhyde), le décylidène glycérol (réaction avec le décanaldéhyde), et le dodécylidène glycérol (réaction avec le dodécanaldéhyde).With regard to the synthesis of long-chain cyclic acetals, mention may be made of the article by G. Stefanovic and G. Petrovic, Bulletin T Liv. from the Serbian Academy of Sciences and Arts, 54 (14) (1976) 53-73, which describes the synthesis of several long-chain glycerol acetals including heptilidene glycerol (reaction with heptanaldehyde), octilidene glycerol (reaction with octanaldehyde), decylidene glycerol (reaction with decanaldehyde), and dodecylidene glycerol (reaction with dodecanaldehyde).
Les acétals de glycérol selon l'invention peuvent être préparés selon différentes autres méthodes : par extraction réactive entre l'aldéhyde et une solution de glycérol, l'acétal produit étant alors moins soluble dans la phase aqueuse peut être facilement extrait et séparé ; par réaction entre le glycérol et l'aldéhyde en lit mobile simulé afin de déplacer fortement les équilibres des réactions d'acétalisation. En vue de leur utilisation dans les carburants diesel, les acétals de l'invention doivent présenter des caractéristiques physiques compatibles avec les normes telles que par exemple la norme française NF EN 590. Les principales caractéristiques sont la masse volumique, la température d'ébullition, le point éclair, la solubilité dans l'eau et l'indice de cétane.The glycerol acetals according to the invention can be prepared according to various other methods: by reactive extraction between the aldehyde and a glycerol solution, the acetal produced then being less soluble in the aqueous phase can be easily extracted and separated; by reaction between the glycerol and the aldehyde simulated moving bed in order to strongly shift the equilibrium of the acetalization reactions. With a view to their use in diesel fuels, the acetals of the invention must have physical characteristics compatible with standards such as, for example, the French standard NF EN 590. Main characteristics are density, boiling point, flash point, solubility in water and cetane number.
Si l'on considère le (2-hexyle-1 ,3-dioxolane-4-yle)méthanol et le 2- hexyle-1 ,3-dioxane-5-ol, qui sont les deux isomères de la réaction d'acétalisation de l'heptanaldéhyde sur le glycérol, on peut observer qu'ils présentent une température d'ébullition de l'ordre de 270-2900C, une faible solubilité dans l'eau convenant à l'application. En outre, ils présentent un point éclair de l'ordre de 1300C et un indice de cétane en mélange particulièrement élevé, de l'ordre de 50, proche de celui exigé pour la base même de carburant diesel.Considering (2-hexyl-1,3-dioxolan-4-yl) methanol and 2-hexyl-1,3-dioxan-5-ol, which are the two isomers of the acetalization reaction of heptanaldehyde on glycerol, it can be observed that they have a boiling point of the order of 270-290 ° C., a low solubility in water suitable for application. In addition, they have a flash point of the order of 130 0 C and a particularly high cetane number of mixture, of the order of 50, close to that required for the very base of diesel fuel.
Les acétals de glycérol à longue chaîne sont particulièrement intéressants car ils ont un indice de cétane élevé ainsi qu'une teneur en oxygène importante (14 à 25 % poids) qui favorise la réduction des émissions de particules conduisant à une réduction des NOx. En outre, ils peuvent être produits à partir de matières premières renouvelables, aussi bien pour le glycérol qui est un coproduit du biodiesel obtenu par transestérification des triglycérides, que pour l'heptanaldéhyde qui peut être obtenu par craquage thermique à partir d'huiles naturelles estérifiées de ricin.The long-chain glycerol acetals are particularly interesting because they have a high cetane number and a high oxygen content (14 to 25% by weight) which promotes the reduction of particulate emissions leading to a reduction of NO x . In addition, they can be produced from renewable raw materials, both for glycerol which is a co-product of biodiesel obtained by transesterification of triglycerides, and for heptanaldehyde, which can be obtained by thermal cracking from esterified natural oils. of castor oil.
Des boosters de cétane peuvent être ajoutés aux coupes gazole typiques, telles qu'utilisées dans la présente invention, de préférence à des teneurs d'au plus 1 % poids. Les boosters de cétane peuvent être sélectionnés parmi les composés nitro et les dialkylperoxydes.Cetane boosters may be added to typical diesel cuts as used in the present invention, preferably at levels of at most 1% by weight. Cetane boosters may be selected from nitro compounds and dialkyl peroxides.
Les compositions de carburant diesel de l'invention sont illustrées par les exemples ci-après. Exemple 1 Préparation d'un mélange entre un gazole et l'acétal.The diesel fuel compositions of the invention are illustrated by the following examples. Example 1 Preparation of a mixture between a gas oil and the acetal.
On prépare l'acétal cyclique par réaction du glycérol sur l'heptanaldéhyde. Une solution aqueuse de glycérol (à 60 % poids de glycérol, 40 % poids d'eau) contenant 10 moles de glycérol (soit 920 g) est mélangée avec 10 moles d'heptanaldéhyde (soit 114 g), soit un ratio molaire heptanaldéhyde/glycérol de 1. Une solution d'acide chlorhydrique à 35 % est ajoutée à la solution aqueuse de glycérol + heptanaldéhyde, dans une proportion de 15 % par rapport au glycérol. Le mélange est alors chauffé et maintenu à 400C pendant 5 heures sous agitation.The cyclic acetal is prepared by reacting glycerol with heptanaldehyde. An aqueous solution of glycerol (60% by weight of glycerol, 40% by weight of water) containing 10 moles of glycerol (ie 920 g) is mixed with 10 moles of heptanaldehyde (ie 114 g) or a molar ratio of heptanaldehyde / glycerol of 1. A solution of 35% hydrochloric acid is added to the aqueous solution of glycerol + heptanaldehyde in a proportion of 15% relative to glycerol. The mixture is then heated and maintained at 40 ° C. for 5 hours. with stirring.
Ensuite, les deux phases sont séparées par décantation, et la phase organique est lavée avec de l'eau, jusqu'à obtenir un pH neutre. La solution obtenue est alors séchée sur MgSO4 anhydre, puis concentrée par évaporation sous vide. Le produit obtenu a été analysé par RMN et spectrométrie de masse et quantifié par analyse chromatographique.Then, the two phases are separated by decantation, and the organic phase is washed with water until a neutral pH. The solution obtained is then dried over anhydrous MgSO 4 and then concentrated by evaporation in vacuo. The product obtained was analyzed by NMR and mass spectrometry and quantified by chromatographic analysis.
On mélange alors l'acétal obtenu avec une base carburant diesel représentative des formulations Euro 2000 : densité de l'ordre de 0,830 à 15°C, teneur en soufre de l'ordre de 290 ppm, indice de cétane de 51 , intervalle de distillation 170-3600C. Le ratio acétal/base carburant est 10 % poids. On mesure alors l'indice de cétane du mélange selon la norme ISO 5165. Celui-ci est légèrement supérieur à 51 ce qui permet de déduire que l'indice de cétane de l'acétal en mélange est de l'ordre de 52. Exemple 2 Essais comparatifs du mélange avec la base carburant diesel. On a effectué des essais ayant pour objectif d'évaluer les performances en matière d'émission de particules des compositions de carburant diesel contenant 10 % poids de l'acétal de glycérol et d'heptanaldéhyde en comparaison avec celles obtenues avec le carburant diesel de référence. Les essais ont été effectués sur un véhicule diesel équipé d'un moteur à injection directe. Ces essais ont été effectués sur le cycle décrit dans la directive européenne 70/220/CE, modifié par la directive 98/69/EC (cycle appelé MVEG-Hs EURO 2000). Ce cycle est composé d'une phase urbaine (cycle EUDC d'une longueur de 4.052 km), et d'une phase extra-urbaine (cycle ECE d'une longueur de 6.955 km). Les résultats des essais, exprimés en milligrammes de particules par kilomètre sont les suivants :The acetal obtained is then mixed with a diesel fuel base representative of Euro 2000 formulations: density of the order of 0.830 at 15 ° C., sulfur content of about 290 ppm, cetane number of 51, distillation interval 170-360 ° C. The acetal / fuel base ratio is 10% by weight. The cetane number of the mixture is then measured according to the ISO 5165 standard. This is slightly greater than 51, which makes it possible to deduce that the cetane number of the acetal in admixture is of the order of 52. 2 Comparative tests of the mixture with the diesel fuel base. Tests were conducted to evaluate particle emission performance of diesel fuel compositions containing 10% by weight of glycerol and heptanaldehyde acetal compared to those obtained with reference diesel fuel. . The tests were conducted on a diesel vehicle equipped with a direct injection engine. These tests were carried out on the cycle described in European Directive 70/220 / EC, amended by Directive 98/69 / EC (called MVEG-Hs EURO 2000 cycle). This cycle is composed of an urban phase (EUDC cycle with a length of 4,052 km), and an extra-urban phase (ECE cycle with a length of 6,955 km). The results of the tests, expressed in milligrams of particles per kilometer are as follows:
Carburant diesel seul : Cycle ECE 65 mg/km, Cycle EUDC 52.5 mg/km, Cycle MVEG 57 mg/km.Diesel fuel only: ECE cycle 65 mg / km, EUDC cycle 52.5 mg / km, MVEG cycle 57 mg / km.
Carburant diesel à 90 % + 10 % d'acétal de glycérol et d'heptanaldéhyde : Cycle ECE 47 mg/km, Cycle EUDC 41 mg/km, Cycle MVEG 43 mg/km. La réduction des émissions de particules avec le carburant selon l'invention est de l'ordre de 25 %. 90% diesel fuel + 10% glycerol and heptanaldehyde acetal: ECE cycle 47 mg / km, EUDC cycle 41 mg / km, MVEG cycle 43 mg / km. The reduction of particulate emissions with the fuel according to the invention is of the order of 25%.

Claims

REVENDICATIONS
1 ) Composition de carburant diesel constituée d'une base de carburant diesel soit d'origine pétrolière, soit d'origine végétale et de 1 à 60 % en poids d'acétals de glycérol caractérisée en ce que l'acétal de glycérol répond à la formule suivante1) Diesel fuel composition consisting of a diesel fuel base either of petroleum origin or of vegetable origin and from 1 to 60% by weight of glycerol acetals, characterized in that the glycerol acetal meets the next formula
dans laquelle Ri est un radical alkyle comprenant de 5 à 13 atomes de carbone dont 5 au moins forment une chaîne linéaire, R2 est soit H, soit un radical alkyle de 1 à 7 atomes de carbone, le nombre total des atomes de carbone de Ri + R2 étant inférieur à 20 et de préférence inférieur à 12. in which R 1 is an alkyl radical comprising from 5 to 13 carbon atoms of which at least 5 form a linear chain, R 2 is either H or an alkyl radical of 1 to 7 carbon atoms, the total number of carbon atoms of R 1 + R2 being less than 20 and preferably less than 12.
2) Composition selon la revendication 1 , caractérisée en ce que Ri est un radical n-alkyle de 6 atomes de carbone.2) Composition according to claim 1, characterized in that R1 is an n-alkyl radical of 6 carbon atoms.
3) Composition selon la revendication 1 , caractérisée en ce que Ri est un radical iso-alkyle de 7 atomes de carbone. 3) Composition according to claim 1, characterized in that R1 is an isoalkyl radical of 7 carbon atoms.
EP07858572A 2006-10-23 2007-10-15 Diesel fuel containing long-chain glycerol acetals Withdrawn EP2094820A2 (en)

Applications Claiming Priority (2)

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FR0654434A FR2907460A1 (en) 2006-10-23 2006-10-23 Diesel fuel composition comprises a petroleum or plant based diesel fuel and glycerol acetals
PCT/FR2007/052145 WO2008050030A2 (en) 2006-10-23 2007-10-15 Diesel fuel containing long-chain glycerol acetals

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FR2833607B1 (en) * 2001-12-19 2005-02-04 Inst Francais Du Petrole DIESEL FUEL COMPOSITIONS CONTAINING GLYCEROL ACETALS
ES2201894B2 (en) * 2002-01-18 2005-03-01 Industrial Management, S.A PROCEDURE TO PRODUCE BIODIESEL FUELS WITH IMPROVED PROPERTIES AT LOW TEMPERATURE.

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