WO2008031965A1 - Diesel fuel compositions containing glycerol acetal esters - Google Patents

Diesel fuel compositions containing glycerol acetal esters Download PDF

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Publication number
WO2008031965A1
WO2008031965A1 PCT/FR2007/051872 FR2007051872W WO2008031965A1 WO 2008031965 A1 WO2008031965 A1 WO 2008031965A1 FR 2007051872 W FR2007051872 W FR 2007051872W WO 2008031965 A1 WO2008031965 A1 WO 2008031965A1
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Prior art keywords
carbon atoms
diesel fuel
glycerol acetal
esters
weight
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PCT/FR2007/051872
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French (fr)
Inventor
Jean-Luc Dubois
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Arkema France
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    • 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
    • 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
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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

Definitions

  • the invention relates to diesel fuel compositions containing oxygenated compounds based on glycerol acetal esters.
  • the object of the invention is to propose the use of glycerol acetal esters as constituents or additives of diesel fuel formulations that make it possible both to optimize use of the engines and to lower pollutant emissions.
  • the subject of the invention is a diesel fuel composition
  • a diesel fuel composition comprising from 50 to 99.9% by weight of a hydrocarbon fuel base or from esters / ethers of polyols and from 0.1 to 50% by weight of at least one ester of glycerol acetal according to at least one of the following formulas:
  • R 1 and R 2 each represent a hydrogen atom or an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, cycloaliphatic or aromatic containing from 1 to 16 carbon atoms, and
  • R 1, R 2 and R 3 are such that they contain in total a maximum of 17 carbon atoms.
  • R 1 and R 2 which are identical or different, are chosen, for example, from the following radicals: H, CH 3 , C 2 H 5 , C 2 H 3 , C 3 H 7 , C 3 H 5 , C 4 H 9 , C 5 Hn , C 6 H 3 , C 7 H 5 , C 8 H 7 ,
  • R 3 is chosen for example from the following radicals: CH 3 , C 2 H 5 , C 2 H 3 , C 3 H 7 ,
  • Ci 7 H 35, C 7 H 33, C 7 H 3I, Ci 7 H 29, C 7 OH 33 It may then be advantageous to choose, as "promoter" of the radical R 3, a fatty acid R 3 COOH of vegetable or animal origin, a renewable raw material.
  • hydrocarbon-based hydrocarbon base means a fuel base comprising one or more substances containing carbon, hydrogen, or possibly sulfur atoms, and less than 2.5% by weight, preferably less 1% by weight of oxygen relative to the total weight of the fuel base.
  • carboxylic acids of this type are given below: acetic, butanoic, hexanoic, octanoic, decanoic, lauric, myristic, palmitic, palmitoleic, stearic, oleic, linoleic, linolenic and ricinoleic acids.
  • the number of carbon atoms carried by all the radicals R 1, R 2 and R 3 will be limited to 17.
  • R 1 and R 2 each represent either a hydrogen atom or a hydrocarbon radical containing from 1 to 11 carbon atoms, and R 3 a radical containing from 1 to 12 carbon atoms. carbon atoms, R 1, R 2 and R 3 being such that they comprise in total a maximum of 12 carbon atoms.
  • the radicals R 1, R 2 will preferably be chosen from hydrogen and the radicals CH 3 , C 2 H 5, C 3 H 7 and C 4 H 9 and R 3 from the radicals CH 3 , C 2 H 5, C 3 H 7 and those derived from light fatty acids of vegetable or animal origin, acids having at most 12 carbon atoms, such as dodecanoic or dodecenoic acids for example.
  • the R 3 chain is selected so as to confer a good compatibility of the product in terms of solubility and boiling temperature with the diesel fuel matrix defined by the French standard NF EN 590.
  • a simple synthesis method consists of reacting an aldehyde and / or a ketone on glycerol in an acidic medium, then, after removal of the water produced, reacting an ester of formula R 3 COOR 4 on the isomers of the acetal glycerol of general formula (3) and (4):
  • a synthetic variant consists in reacting glycerol in an acidic medium with an acetal of formula (OR) 2CRiR 2 and then applying to the glycerol acetals formed the same transesterification reaction as that referred to above.
  • transesterification reaction well known and described in particular in Socha et al., Is generally carried out in an alkaline medium by intermediately forming the sodium or potassium alcoholate.
  • Such an alcoholate can be obtained by reacting the alcohol with sodium hydroxide as described in JP 2003-231686.
  • Another method of synthesis consists in making a reaction between an epoxy group with an aldehyde and / or a ketone using a phosphoric acid-based catalyst, according to the following reaction (2), described for example in US Pat. No. 3,184. 441, US Patent 3,291,860 and by Socha et al.
  • Another method of synthesis is to simultaneously react a carboxylic acid R3COOH with an aldehyde or ketone R1COR2 and glycerol in the presence of a catalyst to directly give the monoglyceride of the acetal.
  • a catalyst to directly give the monoglyceride of the acetal.
  • Such a method of synthesis is for example described in the patent application JP 2001-181271.
  • the catalysts used are organic or inorganic acid catalysts.
  • Another synthetic method similar to the previous one, described in patent application JP 2002-069068, consists in directly reacting the fat (triglyceride) with an aldehyde or a ketone and glycerol in the presence of a catalyst.
  • the glycerol acetal esters of the invention used in the gas oil compositions have formulas (1) and (2) and generally consist of a mixture of these compounds. They can also be a mixture of several esters corresponding to these formulas but having different radicals R 1, R 2 and R 3 .
  • esters of the invention may be mixed with petroleum bases of petroleum origin, essentially hydrocarbon-based or with oxygenated gas oils of plant origin based on alkyl esters and / or plant-derived polyol ethers.
  • the amount of glycerol acetal esters added to the fuel base will generally be between 0.1 and 50% by weight. It will depend on the type of fuel base and the desired effect, a reduction in toxic emissions and / or an improvement in cold operating conditions, fuel viscosity and cold operability.
  • glycerol is reacted with an excess of di-n-propylketone in the presence of an acidic resin.
  • the butanoic ester of the synthesized glycerol acetal has a boiling point of 320 ° C. and a density of 0.960 g / cm 3 , which allows its introduction into a diesel fuel matrix by meeting the standards indicated above.
  • the same process is implemented with the first step of the reaction of a dimethyl ketone on glycerol, then in the second step, a transesterification using methyl ester of dodecanoic acid.
  • the ester of the synthesized glycerol acetal has a boiling point of 375 ° C and a density of 0.950 g / cm 3 , which also allows its use in a diesel base meeting these standards.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

DIESEL FUEL COMPOSITIONS CONTAINING GLYCEROL ACETAL ESTERS. The invention relates to a diesel fuel composition consisting of 50% to 99.9% by weight of a hydrocarbon-based fuel base and/or consisting of polyol esters/ethers and of 0.1% to 50% by weight of at least one glycerol acetal ester having at least one of the following formulae: 10 R3 O R1 O R1 O R2 O O R3 O R2 O O (1) (2) 15 in which R1 and R2 are each either a hydrogen atom, or a saturated or unsaturated, linear or branched aliphatic hydrocarbon-based radical, a cycloaliphatic hydrocarbon-based radical or an aromatic hydrocarbon-based radical containing from 1 to 16 carbon atoms, and R3 is a linear or branched, aliphatic hydrocarbon-based radical comprising from 0 to 3 double bonds C=C and containing from 1 to 17 carbon atoms, wherein R1, R2 and R3 20 are such that they contain in total a maximum of 17 carbon atoms.

Description

COMPOSITIONS DE CARBURANTS DIESEL CONTENANT DES ESTERS D'ACETALS DE GLYCEROL DIESEL FUEL COMPOSITIONS CONTAINING GLYCEROL ACETAL ESTERS
Domaine TechniqueTechnical area
L'invention concerne des compositions de carburants diesel contenant des composés oxygénés à base d'esters d'acétals de glycérol.The invention relates to diesel fuel compositions containing oxygenated compounds based on glycerol acetal esters.
Technique antérieurePrior art
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 les 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 move 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.
Exposé de l'inventionPresentation of the invention
L'objet de l'invention est de proposer l'utilisation d'esters d'acétals de glycérol comme constituants ou additifs de formulations de gazoles permettant à la fois une utilisation optimale des moteurs et un abaissement des émissions polluantes.The object of the invention is to propose the use of glycerol acetal esters as constituents or additives of diesel fuel formulations that make it possible both to optimize use of the engines and to lower pollutant emissions.
L'invention a pour objet une composition de carburant diesel constituée de 50 à 99,9 % poids d'une base carburant hydrocarbonée ou d'esters/éthers de polyols et de 0,1 à 50 % poids d'au moins un ester d'acétal de glycérol répondant à l'une au moins des formules suivantes :The subject of the invention is a diesel fuel composition comprising from 50 to 99.9% by weight of a hydrocarbon fuel base or from esters / ethers of polyols and from 0.1 to 50% by weight of at least one ester of glycerol acetal according to at least one of the following formulas:
Figure imgf000002_0001
Figure imgf000002_0001
(1 ) (2) dans lesquelles :(1) (2) in which :
Ri et R2 représentent chacun soit un atome d'hydrogène, soit un radical hydrocarboné aliphatique, saturé ou non, linéaire ou ramifié, cycloaliphatique ou aromatique comportant de 1 à 16 atomes de carbone, etR 1 and R 2 each represent a hydrogen atom or an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, cycloaliphatic or aromatic containing from 1 to 16 carbon atoms, and
R3 est un radical hydrocarboné aliphatique comprenant de 0 à 3 doubles liaisons C=C, linéaire ou ramifié, comportant de 1 à 17 atomes de carbone,R3 is an aliphatic hydrocarbon radical comprising from 0 to 3 linear or branched C = C double bonds containing from 1 to 17 carbon atoms,
Ri, R2 et R3 étant tels qu'ils comportent au total un maximum de 17 atomes de carbone.R 1, R 2 and R 3 are such that they contain in total a maximum of 17 carbon atoms.
Ri et R2, identiques ou différents, sont choisis par exemple parmi les radicaux suivants : H, CH3, C2H5, C2H3, C3H7, C3H5, C4H9, C5Hn, C6Hi3, C7Hi5, C8Hi7,R 1 and R 2, which are identical or different, are chosen, for example, from the following radicals: H, CH 3 , C 2 H 5 , C 2 H 3 , C 3 H 7 , C 3 H 5 , C 4 H 9 , C 5 Hn , C 6 H 3 , C 7 H 5 , C 8 H 7 ,
C9H19, CnH23, Ci3H27 .C 9 H 19 , CnH 23 , C 13 H 27 .
R3 est choisi par exemple parmi les radicaux suivants : CH3, C2H5, C2H3, C3H7,R 3 is chosen for example from the following radicals: CH 3 , C 2 H 5 , C 2 H 3 , C 3 H 7 ,
C3H5, C4Hg, C5Hn, CeHi3, C7Hi5, CsHi7, C9H19, CnH23, Ci3H27, Ci5H3I, Ci5H2g,C 3 H 5, C 4 Hg, C 5 H n, Cehi 3, C 7 Hi 5, CsHi 7, C 9 H 19, n H 23, C 27 H 3, C 5 H 3I, C 5 H 2 g,
Ci7H35, Ci7H33, Ci7H3I, Ci7H29, Ci7OH33. Il pourra alors être avantageux de choisir comme « promoteur » du radical R3 un acide gras R3COOH d'origine végétale ou animale, matière première renouvelable.Ci 7 H 35, C 7 H 33, C 7 H 3I, Ci 7 H 29, C 7 OH 33. It may then be advantageous to choose, as "promoter" of the radical R 3, a fatty acid R 3 COOH of vegetable or animal origin, a renewable raw material.
Par « base carburant hydrocarbonée » on entend au sens de la présente invention, une base carburant comprenant une ou plusieurs substances renfermant des atomes de carbone, d'hydrogène, éventuellement de soufre, et moins de 2,5% en poids, de préférence moins de 1% en poids d'oxygène par rapport au poids total de la base carburant.For the purposes of the present invention, the term "hydrocarbon-based hydrocarbon base" means a fuel base comprising one or more substances containing carbon, hydrogen, or possibly sulfur atoms, and less than 2.5% by weight, preferably less 1% by weight of oxygen relative to the total weight of the fuel base.
Des exemples d'acides carboxyliques de ce type sont donnés ci-après : acides acétique, butanoïque, hexanoïque, octanoïque, décanoïque, laurique, myristique, palmitique, palmitoléique, stéarique, oléique, linoléique, linolénique et ricinoléique.Examples of carboxylic acids of this type are given below: acetic, butanoic, hexanoic, octanoic, decanoic, lauric, myristic, palmitic, palmitoleic, stearic, oleic, linoleic, linolenic and ricinoleic acids.
Dans une forme préférée de réalisation de l'invention, le nombre d'atomes de carbone portés par l'ensemble des radicaux Ri, R2 et R3 sera limité à 17.In a preferred embodiment of the invention, the number of carbon atoms carried by all the radicals R 1, R 2 and R 3 will be limited to 17.
Dans une autre forme préférée de réalisation de l'invention, Ri et R2 représentent chacun soit un atome d'hydrogène, soit un radical hydrocarboné comportant de 1 à 11 atomes de carbone, et R3 un radical comportant de 1 à 12 atomes de carbone, Ri, R2 et R3 étant tels qu'ils comportent au total un maximum de 12 atomes de carbone.In another preferred embodiment of the invention, R 1 and R 2 each represent either a hydrogen atom or a hydrocarbon radical containing from 1 to 11 carbon atoms, and R 3 a radical containing from 1 to 12 carbon atoms. carbon atoms, R 1, R 2 and R 3 being such that they comprise in total a maximum of 12 carbon atoms.
Dans ce cas, les radicaux Ri, R2 seront de préférence choisis parmi l'hydrogène et les radicaux CH3, C2H5, C3H7 et C4H9 et R3 parmi les radicaux CH3, C2H5, C3H7 et ceux provenant d'acides gras légers d'origine végétale ou animale, acides comportant au plus 12 atomes de carbone, tels que les acides dodécanoïque ou dodécènoïque par exemple.In this case, the radicals R 1, R 2 will preferably be chosen from hydrogen and the radicals CH 3 , C 2 H 5, C 3 H 7 and C 4 H 9 and R 3 from the radicals CH 3 , C 2 H 5, C 3 H 7 and those derived from light fatty acids of vegetable or animal origin, acids having at most 12 carbon atoms, such as dodecanoic or dodecenoic acids for example.
La chaîne R3 est sélectionnée de manière à conférer une bonne compatibilité du produit en matière de solubilité et de température d'ébullition avec la matrice du gazole définie par la norme française NF EN 590.The R 3 chain is selected so as to confer a good compatibility of the product in terms of solubility and boiling temperature with the diesel fuel matrix defined by the French standard NF EN 590.
La synthèse des esters d'acétals de glycérol de l'invention se réalise selon des réactions bien connues et décrites notamment dans les références citées ci-dessous.The synthesis of the glycerol acetal esters of the invention is carried out according to well-known reactions and described in particular in the references cited below.
Une méthode de synthèse simple consiste à faire réagir en milieu acide un aldéhyde et/ou une cétone sur le glycérol, puis, après élimination de l'eau produite, à réagir un ester de formule R3COOR4 sur les isomères de l'acétal de glycérol de formule générale (3) et (4) :A simple synthesis method consists of reacting an aldehyde and / or a ketone on glycerol in an acidic medium, then, after removal of the water produced, reacting an ester of formula R 3 COOR 4 on the isomers of the acetal glycerol of general formula (3) and (4):
Figure imgf000004_0001
Figure imgf000004_0001
(3) (4) issus de la réaction précédente pour obtenir par transestérification les esters d'acétal de glycérol de l'invention. Cette méthode de préparation est par exemple décrite par Socha et al dans Journal of Applied Polymer Science (2001 ), 81 (12), 2875-2880 et Hochberg, SJ dans Coating Technol. 1965 pages 1043-1067. et met en œuvre le mécanisme réactionnel (1) ci-dessous :(3) (4) from the above reaction to obtain by transesterification the glycerol acetal esters of the invention. This method of preparation is for example described by Socha et al in Journal of Applied Polymer Science (2001), 81 (12), 2875-2880 and Hochberg, SJ in Coating Technol. 1965 pages 1043-1067. and implements the reaction mechanism (1) below:
( 1 )
Figure imgf000005_0001
(1)
Figure imgf000005_0001
Une variante de synthèse consiste à faire réagir en milieu acide le glycérol avec un acétal de formule (OR)2CRiR2, puis à appliquer aux acétals de glycérol formés la même réaction de transestérification que celle visée ci- dessus.A synthetic variant consists in reacting glycerol in an acidic medium with an acetal of formula (OR) 2CRiR 2 and then applying to the glycerol acetals formed the same transesterification reaction as that referred to above.
La réaction de transestérification bien connue et décrite notamment dans Socha et al., s'effectue en général en milieu alcalin en formant de façon intermédiaire l'alcoolate de sodium ou de potassium. Un tel alcoolate peut être obtenu en faisant réagir l'alcool sur de l'hydroxyde de sodium tel que décrit dans la demande JP 2003-231686.The transesterification reaction well known and described in particular in Socha et al., Is generally carried out in an alkaline medium by intermediately forming the sodium or potassium alcoholate. Such an alcoholate can be obtained by reacting the alcohol with sodium hydroxide as described in JP 2003-231686.
Une autre méthode de synthèse consiste à faire une réaction entre un groupement époxy avec un aldéhyde et/ou une cétone en utilisant un catalyseur à base d'acide phosphorique, selon la réaction (2) suivante, décrite par exemple dans le brevet US 3 184 441 , le brevet US 3 291 860 et par Socha et al.Another method of synthesis consists in making a reaction between an epoxy group with an aldehyde and / or a ketone using a phosphoric acid-based catalyst, according to the following reaction (2), described for example in US Pat. No. 3,184. 441, US Patent 3,291,860 and by Socha et al.
Figure imgf000005_0002
Figure imgf000005_0002
(2) Une autre méthode de synthèse consiste à faire réagir simultanément un acide carboxylique R3COOH avec un aldéhyde ou une cétone R1COR2 et du glycérol en présence d'un catalyseur pour donner directement le monoglycéride de l'acétal. Une telle méthode de synthèse est par exemple décrite dans la demande de brevet JP 2001-181271. Les catalyseurs utilisés sont des catalyseurs acides organiques ou minéraux.(2) Another method of synthesis is to simultaneously react a carboxylic acid R3COOH with an aldehyde or ketone R1COR2 and glycerol in the presence of a catalyst to directly give the monoglyceride of the acetal. Such a method of synthesis is for example described in the patent application JP 2001-181271. The catalysts used are organic or inorganic acid catalysts.
Une autre méthode de synthèse similaire à la précédente, décrite dans la demande de brevet JP 2002-069068, consiste à faire réagir directement la matière grasse (triglycéride) avec un aldéhyde ou une cétone et du glycérol en présence d'un catalyseur.Another synthetic method similar to the previous one, described in patent application JP 2002-069068, consists in directly reacting the fat (triglyceride) with an aldehyde or a ketone and glycerol in the presence of a catalyst.
Une autre méthode de synthèse est décrite dans le brevet US3686238 et consiste à faire réagir le chlorure d'acide avec l'acétal de glycérol en présence d'une base telle la triéthylamine ou la pyridine.Another method of synthesis is described in US Pat. No. 3,686,238 and consists in reacting the acid chloride with the glycerol acetal in the presence of a base such as triethylamine or pyridine.
Les esters d'acétals de glycérol de l'invention utilisés dans les compositions de gazole répondent aux formules (1 ) et (2) et sont généralement constitués d'un mélange de ces composés. Ils peuvent également être un mélange de plusieurs esters répondant à ces formules mais comportant des radicaux Ri, R2 et R3 différents.The glycerol acetal esters of the invention used in the gas oil compositions have formulas (1) and (2) and generally consist of a mixture of these compounds. They can also be a mixture of several esters corresponding to these formulas but having different radicals R 1, R 2 and R 3 .
Les esters de l'invention peuvent être mélangés avec des bases carburants d'origine pétrolière, essentiellement hydrocarbonées ou avec des gazoles oxygénés d'origine végétale à base d'esters alkyliques et/ou d'éthers de polyols d'origine végétale.The esters of the invention may be mixed with petroleum bases of petroleum origin, essentially hydrocarbon-based or with oxygenated gas oils of plant origin based on alkyl esters and / or plant-derived polyol ethers.
La quantité d'esters d'acétals de glycérol ajoutés à la base carburant sera généralement comprise entre 0,1 et 50 % en poids. Elle dépendra du type de base carburant et de l'effet recherché, une diminution des émissions toxiques et/ou une amélioration des conditions de fonctionnement à froid, viscosité du carburant et opérabilité à froid.The amount of glycerol acetal esters added to the fuel base will generally be between 0.1 and 50% by weight. It will depend on the type of fuel base and the desired effect, a reduction in toxic emissions and / or an improvement in cold operating conditions, fuel viscosity and cold operability.
ExemplesExamples
Dans une première étape on fait réagir du glycérol avec un excès de di n-propylcétone en présence d'une résine acide. L'acétal de glycérol ainsi obtenu qui répond aux formules (3) et (4) avec Ri = R2 = C3H7 est ensuite séparé de l'excès de cétone puis, ensuite dans une deuxième étape, soumis à une réaction de transestérification au moyen de l'ester méthylique de l'acide butanoïque. L'ester butanoïque de l'acétal de glycérol synthétisé a un point d'ébullition de 3200C et une masse volumique de 0,960 g/cm3, qui permet son introduction dans une matrice de gazole en répondant aux normes indiquées précédemment.In a first step glycerol is reacted with an excess of di-n-propylketone in the presence of an acidic resin. The glycerol acetal thus obtained which corresponds to formulas (3) and (4) with R 1 = R 2 = C 3 H 7 is then separated from the excess ketone and then, in a second step, subjected to a transesterification reaction using methyl butanoic acid ester. The butanoic ester of the synthesized glycerol acetal has a boiling point of 320 ° C. and a density of 0.960 g / cm 3 , which allows its introduction into a diesel fuel matrix by meeting the standards indicated above.
Le même processus est mis en œuvre avec en première étape la réaction d'une diméthyle cétone sur le glycérol, puis en deuxième étape, une transestérification au moyen de l'ester méthylique de l'acide dodecanoïque. L'ester de l'acétal de glycérol synthétisé a un point d'ébullition de 375°C et une masse volumique de 0,950 g/cm3, qui permet également son utilisation dans une base gazole répondant auxdites normes. The same process is implemented with the first step of the reaction of a dimethyl ketone on glycerol, then in the second step, a transesterification using methyl ester of dodecanoic acid. The ester of the synthesized glycerol acetal has a boiling point of 375 ° C and a density of 0.950 g / cm 3 , which also allows its use in a diesel base meeting these standards.

Claims

REVENDICATIONS
1 ) Composition de carburant diesel constituée de 50 à 99,9 % poids d'une base carburant hydrocarbonée et de 0,1 à 50 % poids d'au moins un ester d'acétal de glycérol répondant à l'une au moins des formules suivantes :1) Diesel fuel composition comprising from 50 to 99.9% by weight of a hydrocarbon fuel base and from 0.1 to 50% by weight of at least one glycerol acetal ester corresponding to at least one of the formulas following:
Figure imgf000008_0001
Figure imgf000008_0001
(1 ) (2) dans lesquelles Ri et R2 représentent chacun soit un atome d'hydrogène, soit un radical hydrocarboné aliphatique, saturé ou non, linéaire ou ramifié, cycloaliphatique ou aromatique comportant de 1 à 16 atomes de carbone, et R3 est un radical hydrocarboné aliphatique comprenant de 0 à 3 doubles liaisons C=C, linéaire ou ramifié, comportant de 1 à 17 atomes de carbone, Ri, R2 et R3 étant tels qu'ils comportent au total un maximum de 17 atomes de carbone.(1) (2) in which R 1 and R 2 each represent a hydrogen atom or an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, cycloaliphatic or aromatic containing from 1 to 16 carbon atoms, and R 3 is an aliphatic hydrocarbon radical comprising from 0 to 3 linear or branched C = C double bonds, comprising from 1 to 17 carbon atoms, R 1, R 2 and R 3 being such that they comprise in total a maximum of 17 carbon atoms.
2) Composition selon la revendication 1 , dans laquelle Ri et R2 représentent chacun soit un atome d'hydrogène, soit un radical hydrocarboné comportant de 1 à 11 atomes de carbone, et R3 un radical comportant de 1 à 12 atomes de carbone, Ri, R2 et R3 étant tels qu'ils comportent au total un maximum de 12 atomes de carbone.2) The composition according to claim 1, in which R 1 and R 2 each represent a hydrogen atom or a hydrocarbon radical containing from 1 to 11 carbon atoms, and R 3 a radical containing from 1 to 12 carbon atoms, R 1, R 2 and R 3 being such that they comprise in total a maximum of 12 carbon atoms.
3) Composition selon la revendication 1 ou 2 caractérisée en ce qu'elle est constituée en outre d'esters/ethers de polyols. 3) Composition according to claim 1 or 2 characterized in that it is further composed of esters / ethers of polyols.
PCT/FR2007/051872 2006-09-13 2007-09-05 Diesel fuel compositions containing glycerol acetal esters WO2008031965A1 (en)

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FR0653713A FR2905703A1 (en) 2006-09-13 2006-09-13 DIESEL FUEL COMPOSITIONS CONTAINING GLYCEROL ACETAL ESTERS
FR06.53713 2006-09-13

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010053354A2 (en) * 2008-11-05 2010-05-14 Criss Cross Technology Bv A motor fuel additive with enhanced properties, and processes for the production thereof
CN102977937A (en) * 2012-11-23 2013-03-20 占小玲 Blended fuel for vehicles
WO2017006141A1 (en) * 2015-07-06 2017-01-12 Rhodia Poliamida E Especialidades Ltda Diesel compositions with improved cetane number and lubricity performances

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1321503A1 (en) * 2001-12-19 2003-06-25 Institut Francais Du Petrole Diesel fuel compositions containing glycerol acetal carbonates
WO2006084048A1 (en) * 2005-02-02 2006-08-10 Jalin Technologies, Llc Bio-diesel fuel and manufacture of same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1321503A1 (en) * 2001-12-19 2003-06-25 Institut Francais Du Petrole Diesel fuel compositions containing glycerol acetal carbonates
WO2006084048A1 (en) * 2005-02-02 2006-08-10 Jalin Technologies, Llc Bio-diesel fuel and manufacture of same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010053354A2 (en) * 2008-11-05 2010-05-14 Criss Cross Technology Bv A motor fuel additive with enhanced properties, and processes for the production thereof
WO2010053354A3 (en) * 2008-11-05 2010-11-04 Criss Cross Technology Bv A motor fuel additive with enhanced properties, and processes for the production thereof
CN102977937A (en) * 2012-11-23 2013-03-20 占小玲 Blended fuel for vehicles
WO2017006141A1 (en) * 2015-07-06 2017-01-12 Rhodia Poliamida E Especialidades Ltda Diesel compositions with improved cetane number and lubricity performances
WO2017006167A1 (en) * 2015-07-06 2017-01-12 Rhodia Poliamida E Especialidades Ltda Diesel compositions with improved cetane number and lubricity performances
CN107835849A (en) * 2015-07-06 2018-03-23 罗地亚聚酰胺特殊品公司 With the Dresel fuel compositions for improving Cetane number and greasy property
US11072753B2 (en) 2015-07-06 2021-07-27 Rhodia Poliamida E Especialidades S.A. Diesel compositions with improved cetane number and lubricity performances

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