EP0923628A1

EP0923628A1 - Fuel composition for diesel engines containing oxygenated compounds

Info

Publication number: EP0923628A1
Application number: EP98929517A
Authority: EP
Inventors: Laurent Germanaud; Paul Maldonado; Paul Bourdauducq; Jean-Luc Couturier
Original assignee: Elf Antar France
Current assignee: Total Marketing Services SA
Priority date: 1997-06-09
Filing date: 1998-06-08
Publication date: 1999-06-23
Anticipated expiration: 2018-06-08
Also published as: NO990578L; JP2000516991A; EP0923628B1; WO1998056879A1; ES2189188T3; DE69810746T2; DK0923628T3; DE69810746D1; FR2764301B1; ATE231179T1; US6113661A; FR2764301A1; NO990578D0

Abstract

PCT No. PCT/FR98/01168 Sec. 371 Date May 4, 1999 Sec. 102(e) Date May 4, 1999 PCT Filed Jun. 8, 1998 PCT Pub. No. WO98/56879 PCT Pub. Date Dec. 17, 1998A fuel composition containing, as a major portion, at least one fuel base, and, as a minor portion, at least one oxygenated compound, which contains at least 0.05% by weight of at least one trialkoxyalkane of the formula (I): wherein: X is a divalent hydrocarbon-containing group CnH2n, wherein n is 1, 2, or 3, each hydrogen atom optionally being substituted by a hydrocarbon-containing residue; R1, R'1, and R''1 are each independently linear or branched alkyl groups containing from 1 to 10 carbon atoms and optionally at least one oxygen atom, two of each of R1, R'1 and R''1 groups optionally being connected to form a heterocyclic ring containing 5 or 6 atoms; and R2 is a hydrogen atom or a linear C1-C4 alkyl radical, or R2 and hydrocarbon-containing residue X, together by bonding, form a ring containing 5 or 6 carbon atoms.

Description

FUEL COMPOSITION COMPRISING OXYGENIC COMPOUNDS

FOR DIESEL ENGINES

The present invention relates to a new fuel composition comprising oxygenated compounds improving the combustion of fuel, in particular compounds which can improve the cetane number of fuel bases such as middle distillates used in the composition of gas oils for diesel engines.

It is well known to introduce oxygenated components into gasolines to improve the octane number, such as MTBE, 1 ETBE and others to replace in particular the lead which was introduced there in the past. For diesel, we are not talking about an octane number but rather a cetane number corresponding like octane to a characteristic of combustion of fuel in a combustion engine. This cetane number represents more particularly the ability of the fuel base to self-ignite in the combustion chamber of the engine. Too low a cetane number corresponds to a too long self-ignition delay which generates late, brutal and incomplete combustion with formation of unburnt. This poor combustion results in an increase in polluting emissions from the exhaust, an increase in noise corresponding to the auto-ignition of the fuel, in particular when the engine is running at idle, and greater difficulties in starting the engine, in particular in cold, since combustion is delayed. It is therefore preferable for the proper functioning of diesel engines to have a fuel with a high cetane number. However, this high cetane depends on the nature of the fuel base used and on the nature and effectiveness of the so-called pro-cetane or cetane improving additives which it is necessary to add to these bases.

A fuel base is generally constituted by a physical mixture of several middle distillates or petroleum fractions resulting from the refining of crude oils originating from all walks of the world. These petroleum fractions come from a large number of separations by atmospheric or vacuum distillation and from chemical transformations of some of these distilled cuts by hydrodesulfurization and or catalytic cracking. By an appropriate mixture of these different refined cuts, a large variety of fuel bases with relatively different physicochemical properties is obtained. Finally, diesel or diesel fuels usable in combustion engines are prepared by a complex mixture of these bases. However, to obtain fuels that meet current legal specifications, refiners must develop increasingly complicated formulations that favor crude oils with a high concentration of distillates and fuel bases with a high cetane number.

The small quantity of easily accessible refined cuts, with a sufficiently high cetane number, forced the refiners to seek additives or components which, in mixture with these cuts, are capable of increasing the cetane number.

Among the additives, that is to say the compounds introduced at low contents into the refined cuts, it is known to use nitrates or organic peroxides which it is known that they have a limited effectiveness in fuel bases or gas oils naturally having a low cetane number. In addition, the organic peroxides decompose irreversibly as a function of time, which leads to a deterioration in the characteristics of the diesel fuel stored both in terms of quality and of cetane number.

Refiners have long been looking for other sources of compounds which can make it possible to improve the cetane number of fuel bases and diesel fuels, in particular among oxygenated compounds such as ethers, polyethers or even acetals. The addition of oxygenated compounds in diesel fuels makes it possible to reduce the emission of pollutants, in particular the emission of particles (EP 14.992). Thus, US Pat. No. 5,308,365 claims the addition of 1 to 30% by weight of dialkylated and trialkylated derivatives of glycerin, obtained by adding an olefin such as isobutene to glycerol, in a gas oil having a range of use between 160 ° C and 370 ° C and a sulfur content less than or equal to 500 ppm.

US Pat. No. 5,425,790 claims the use of an additive of general formula H- (0A) _n -H or A is of ethylene structure substituted with a methyl or ethyl group and n is an integer between 10 and 25.

Patent JP 0725 8661 claims a formulation comprising 20 to 94% of a diesel cut having a distillation range between 130 ° C and 400 ° C, 5 to 40% of a hydrocracked diesel cut commonly called LCO and 1 to 40 % of a monoether of formula R ₁ OR ₂ in which R ^ and R ₂ are alkyl chains of 3 to 12 carbon atoms.

Patent JP 0701 8271 claims gas oils containing ether glycols of formula R ₁ - (OA) _n -R ₂ in which R is an alkyl chain of 1 to 10 carbon atoms, R ₂ represents the hydrogen atom or a alkyl chain comprising from 1 to 10 carbon atoms, A is of ethylene or trimethylene structure optionally substituted and n is an integer varying from 1 to 10.

Patent JP 0634 0886 claims the addition to a diesel of 0.05% to 20% by weight of a compound of general formula Ri-O- (EO) _n - (PO) _m -R ₂ in which R _x and R ₂ represent independently the hydrogen atom or an alkyl chain comprising from 1 to 20 carbon atoms, EO and PO representing respectively the oxyethylene and oxyisopropylene groups, and, m and n are integers between 0 and 15.

On the other hand, patent FR 2,544,738 claims, as a component of diesel fuels, acetals of formula C ₄ Hg-0-CR ₁ R2-0-C H9 R- _j _ and R which may be hydrogen or an alkyl group.

However, these compounds of the prior art, in particular low molecular weight acetals or alternatively ethers containing several oxygen atoms, have a major drawback linked to their high hydrophilic nature, favoring the trapping of water in fuels. However, it is well known that the water in fuels generates corrosion and wear of the mechanical parts, and, moreover, that it promotes the development of bacteria in the circuit which clogs the filters and the systems of power supply, resulting in engine malfunction.

Another drawback of these oxygenated compounds, in particular ethers and polyethers, is linked to their method of manufacture in several stages which makes them expensive and limits their continuous manufacture on a large scale.

The present invention relates to the use of a new family of oxygenated compounds in diesel fuels, which make it possible to increase the cetane index, to provide greater flexibility in the formulation of diesel fuels for a lower cost and also make it possible to limit the aromatic and sulfur compounds responsible for the emission of particles. The present invention therefore relates to a fuel composition comprising a major part of at least one fuel base and a minor part of at least one oxygenated compound characterized in that it contains at least 0.05% by weight of at least one trialkoxyalkane of general formula (I) below:

in which ;

X corresponds to a divalent hydrocarbon group C H of which n is equal to 1, 2 or 3, each hydrogen atom being optionally substituted by a hydrocarbon residue,

• R, R 'and R''are identical or different linear or branched alkyl groups comprising from 1 to 10 carbon atoms and optionally at least one oxygen atom, two of the groups R ^, R' i and R ''^ being optionally linked to form a heterocycle of 5 to 6 atoms;

• and R being a hydrogen atom or a linear alkyl radical comprising from 1 to 4 carbon atoms, R possibly even forming, by bond with a hydrocarbon residue of X, a ring comprising from 5 to 6 carbon atoms.

In the context of the present invention, this fuel composition contains from 60 to 99.95% by weight of at least one fuel base and from 0.05 to 40% by weight of trialkoxyalkane of formula (I).

By fuel base is meant any petroleum cut after refining, either by distillation or by treatment of these distilled cuts.

In a first embodiment of the invention, the trialkoxyalkane is chosen from the trialkoxypropanes of formula (II) below:

^R 4? 3 0 - R '

1 1 "l

Ri 0 C • - CC 1HH - - CC - 0 0 - RR ¹ 'i (n:

1 1

R '4 R ₂ in which;

• R- _j _, R ' _Q _ and R''ι are linear or branched alkyl groups, identical or different comprising from 1 to 10 carbon atoms and optionally at least one oxygen atom, two of the groups R _{1 #} R'-L and R''ι being optionally linked to form a heterocycle of 5 to 6 atoms;

• R2, R3, R4 and R'4 are identical or different groups representing hydrogen or a linear alkyl radical comprising from 1 to 4 carbon atoms, R possibly even forming, by bond with R or R ' _4, a ring comprising 5 to 6 carbon atoms.

In a first embodiment of the invention, in formula (II), R ₂ , R ₃ , R ₄ and R ' ₄ are the hydrogen atom. In a first variant of this first mode, R ₁ , R'- _L and R '' are identical and are chosen from alkyl groups comprising from 1 to 4 carbon atoms.

The trialkoxyalkane compounds thus obtained of the invention are chosen from the group consisting of trimethoxypropane, triethoxypropane, tripropoxypropane, tributoxypropane.

In a second variant of this first mode, ^R _l ' ^R ' _l ^{and R} '' _l comprise from 1 to 4 carbons and at least one oxygen atom.

Among the compounds thus constituted, one will preferably choose from the group consisting of tri (methoxyethoxy) propane and tri (ethoxyethoxy) propane.

In a third variant of this first mode, R ₁ is an alkyl group comprising from 1 to 4 carbon atoms and R ' _] _ and R''i are linked and constitute a link of 2 to 3 carbons so as to form with the two oxygen atoms a heterocycle of 5 to 6 atoms. Among these compounds, 2- (2-hydroxyethyl) ethoxy-1,3,3-dioxolane is preferred.

In a second embodiment of the invention, in formula (II), R ₄ is an alkyl group of 1 to 4 carbon atoms, R ₂ , R ₃ and R ' ₄ are hydrogen atoms and RL, R'-L and R '' 1 are alkyl groups comprising from 1 to 5 carbon atoms.

Among the compounds thus defined, 1, 1, 3-trimethoxybutane, 1, 1, 3-triethoxybutane, 1,1,3-tripropoxybutane and 1, 1, 3-tributoxybutane are preferred.

In a third preferred embodiment of the invention, in formula (II) R ₂ or R ₃ is an alkyl group comprising

1 to 4 carbon atoms, R ₄ , R ' ₄ and, R ₂ or R ₃ , are hydrogen atoms, and R _{1 (} R'-L and R' are alkyl groups comprising from 1 to 5 atoms carbon.

Among the preferred compounds of this variant, 1, 1, 3-triethoxy-2-methylpropane and 1, 3, 3-triethoxybutane are preferred. In a fourth embodiment of the invention, in formula (II), R ₃ and R ₄ are hydrogen atoms, R ₂ and R ' ₄ are linked to form a saturated ring comprising from 5 to 6 atoms of carbon, R _] _, R'-L and R '' _i are alkyl groups comprising from 1 to 5 carbon atoms.

Among the compounds constituting this variant of the invention, 1, 1, 3-triethoxycyclohexane is preferred.

To implement the invention, the fuel bases are chosen from refined cuts distilling between 170 and 370 ° C. containing at most 50% by weight of aromatics, and less than 0.2% by weight of sulfur-containing compounds.

The examples below are given by way of illustration but not limit the invention.

EXAMPLE I Preparation of 1, 1, 3-triethoxypropane

The synthesis of 1, 1, 3-triethoxypropane was carried out according to a patent FR 1,447,138 of January 30, 1964. The catalyst used for the reaction is an acid sulfonic resin. The final neutralization, which was not mentioned in this patent, is carried out with a basic resin. 800g of absolute ethanol (17.4 mol) and 25g of Amberlyst® 15 resin (Aldrich), previously washed with ethanol and dried, are charged to a 2L reactor. At 50 ° C., 185 g of acrolein (3.3 mol) are introduced over a period of 4 hours. At the end of the addition, the mixture is left to react for 3 hours at 50 ° C. The reaction mixture is filtered, neutralized with stirring for one hour with 8 g of Amberlyst® A21 resin (Aldrich, previously washed with ethanol), then filtered again. After distillation (T _eb = 75-78 ° C / 25 mbar), 390 g of 1, 1, 3-triethoxypropane are obtained (Yield = 67%). EXAMPLE 2

The cetane number of the 1,3,3-triethoxypropane prepared according to example 1 was measured according to standard ASTM D613, as a 20% mixture in two gas oils whose characteristics are indicated below:

TABLE I

The cetane index IC of pure 1, 1, 3-triethoxypropane is deduced from the measured value of cetane of the mixture, assuming a linear mixing law, according to the equation: IC (1, 1, 3-triethoxypropane) ₌ TC mixture - 0.8 TC gas l

0.2

TABLE II

EXAMPLE 3

In this example, the cetane number, the boiling point and the water solubility of the 1,3-triethoxy-propane and those of components already known or cited in the prior art were compared.

A compound having a cetane number greater than 70, and a boiling point of at least 160 ° C and a very low solubility in water can be considered as an ideal component usable in diesel.

TABLE III

Claims

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- Fuel composition comprising a major part of at least one fuel base and a minor part of at least one oxygenated compound characterized in that it contains at least 0.05% by weight of at least one trialkoxyalkane of general formula (I) below:

in which ;

• X corresponds to a divalent hydrocarbon group

C H of which n is equal to 1, 2 or 3, each n 2n hydrogen atom being optionally substituted by a hydrocarbon residue,

• R, R 'and R''are identical or different linear or branched alkyl groups comprising from 1 to 10 carbon atoms and optionally at least one oxygen atom, two of the groups R- _] _, R'-L and R''ι being optionally linked to form a heterocycle of 5 to 6 atoms;

• and R being a hydrogen atom or a linear alkyl radical comprising from 1 to 4 carbon atoms, R possibly even forming, by bond with a hydrocarbon residue of X, a ring comprising from 5 to 6 carbon atoms;

- Fuel composition according to claim 1 characterized in that it contains from 60 to 99.95% by weight of at least one fuel base and from 0.05 to 40% by weight of trialkoxyalkane of formula (I).

- Fuel composition according to either of Claims 1 and 2, characterized in that the trialkoxyalkane is chosen from the trialkoxypropanes of formula (II) below: in which ;

• R, R 'and R''are identical or different linear or branched alkyl groups comprising from 1 to 10 carbon atoms and optionally at least one oxygen atom, two of the groups R _{1 #} R'-L and R '' ι being optionally connected to form a heterocycle of 5 to 6 atoms;

• R, R, R and R 'are identical or different groups representing hydrogen or a linear alkyl radical comprising from 1 to 4 carbon atoms, R possibly even forming, by bond with R ₄ or R' _4, a ring comprising 5 to 6 carbon atoms.

4 - Fuel composition according to claim 3 characterized in that R, R, R and R 'in the formula

^ 2 3 4 4

(II) correspond to a hydrogen atom

5 - Fuel composition according to one of claims 3 and 4 characterized in that R, R 'and R' 'are identical and are chosen from alkyl groups comprising from 1 to 4 carbon atoms.

6 - Fuel composition according to claims 3 to 5 characterized in that the compounds of formulas (II) are chosen from the group consisting of trimethoxypropane, triethoxypropane, tripropoxypropane, tributoxypropane.

7 - Fuel composition according to claims 3 and 4 characterized in that R, R 'and R' 'comprise from 1 to

4 carbons and at least one oxygen atom. - Fuel composition according to claims 3, 4 and 7 characterized in that the compounds of formulas (II) are chosen from the group consisting of tri (methoxyethoxy) propane and tri (ethoxyethoxy) propane.

- Fuel composition according to claims 3 and 4 characterized in that R ₁ is an alkyl group comprising from 1 to 4 carbon atoms and R'- and R 7 are linked and constitute a chain of 2 to 3 carbon so as to form with the two oxygen atoms a heterocycle of 5 to 6 atoms.

- Fuel composition according to claims 3, 4 and 9 characterized in that the compound of formula (II) is 2- (2-hydroxyethyl) ethoxy-1, 3-dioxolane.

- Fuel composition according to claim 3 characterized in that in formula (II), R is an alkyl group comprising from 1 to 4 carbon atoms, and, R, R ₃ and R ' ₄ are hydrogen atoms, and R _{1 (} R'-L and R '' 1 are alkyl groups comprising from 1 to 5 carbon atoms.

- Fuel composition according to claims 3 and

11 characterized in that the compounds of formulas (II) are chosen from the group consisting of 1,1,3- trimethoxybutane, 1, 1, 3-triethoxybutane, 1,1,3- tripropoxybutane and 1, 1 , 3-tributoxybutane.

- Fuel composition according to claim 3 characterized in that in formula (II), R ₂ or R ₃ is an alkyl group comprising 1 to 4 carbon atoms, R ₄ , R ' ₄ and, R ₂ or R ₃ , are hydrogen atoms, and RL, R'-L and R '' are alkyl groups comprising from 1 to 5 carbon atoms. - Fuel composition according to claims 3 and

13 characterized in that the compounds of formula (II) are chosen from the group consisting of 1,1,3-triethoxy-2-methylpropane and 1, 3, 3-triethoxybutane.

- Fuel composition according to claim 3 characterized in that in formula (II), R ₃ and R ₄ are hydrogen atoms, R ₂ and R 'are linked to form a saturated ring comprising from 5 to 6 atoms of carbon, R _{1 #} R ' _x and R''are alkyl groups comprising from 1 to 5 carbon atoms.

- Fuel composition according to claims 3 and 15 characterized in that the compound of formula (II) is 1, 1, 3-triethoxycyclohexane.