EP2732012B1 - Compositions of additives improving stability and engine performance of diesel fuels. - Google Patents

Description

Technical area

The present invention relates to additive compositions for improving the stability and engine performance of gas oils used as diesel fuel, particularly non-road type gas oils.

Since the entry into force of the decree of 10 December 2010, is called in France "non-road diesel" a mixture of hydrocarbons of mineral or synthetic origin and 7 parts by volume of methyl esters of fatty acids in accordance with the minimum requirements of EN 590 or any other applicable EU standard or specification at the distribution stage, a maximum sulfur content of 20 mg / kg.

Before, domestic fuel (fod) was intended for both heating applications and motor applications; since this Order, the products are differentiated, ie distributed in different distribution networks and must be stored in separate storage facilities in different networks depending on their destination: stationary applications (heating) on the one hand, and non-stationary applications (non-stationary road). For heating applications, the fuel oil has a sulfur content of 1,000 pm mass while the non-road diesel has a sulfur content of less than or equal to 10 ppm mass (tolerance 20 ppm); the cetane index of domestic fuel is 40 while that of non-road diesel is 51 (better flammability).

• * les engins mobiles non routiers, tels que
  • équipements de construction et travaux publics, notamment bulldozers, camions tout terrain, excavateurs tracteurs et chargeuses,
  • équipements d'entretien des routes
  • chasse-neige et balayeuses urbaines,
  • machines agricoles automotrices, équipements de sylviculture,
  • équipements de manutention, grues mobiles, chariots élévateurs,
  • échelles et nacelles automotrices,
  • équipements d'assistance aéroportuaire au sol
  • équipements industriels de forage,
  • compresseurs et motopompes,
  • locomotives ferroviaires,
  • groupes électrogènes ou hydrauliques sur camion,
• * les tracteurs agricoles ou forestiers,
• * les bateaux de plaisance,
• * les bateaux de navigation intérieure.

The use of non-road diesel, marketed via a specific distribution network and subject to taxation different from that of motor vehicles, is mandatory in France for

• * non-road mobile machinery, such as
  • construction and public works equipment, including bulldozers, off-road trucks, tractor and loader excavators,
  • road maintenance equipment
  • snow plow and street sweepers,
  • self-propelled agricultural machinery, forestry equipment,
  • handling equipment, mobile cranes, forklifts,
  • ladders and self-propelled platforms,
  • airport ground support equipment
  • industrial drilling equipment,
  • compressors and motor pumps,
  • railway locomotives,
  • truck-mounted generators or hydraulic generators,
• * agricultural or forestry tractors,
• * pleasure boats,
• * Inland navigation vessels.

For environmental reasons and / or availability of resources, regulations in many countries encourage the introduction of ever-increasing amounts of renewable products, such as fatty acid esters, into conventional and non-conventional diesel. road. Thus, currently in the EU, road diesel used as diesel fuel may contain 7 parts by volume of fatty acid esters, in general fatty acid methyl esters (FAMEs), essentially or exclusively of plant or animal origin. (esters of vegetable and / or animal oils, in particular methyl esters of vegetable oils or VOMEs).

State of the art

In the past, the engines of non-road diesel engines were considered rustic and undemanding, but the engines of these machines have evolved and function more and more according to such advanced technologies. (direct injection technologies at very high pressure) than those of motor vehicles traveling on the roads.

• stabilité au stockage et en utilisation : en cas de stockage prolongé ou en cas d'utilisation dans des conditions de pressions ou températures élevées : les antioxydants incorporés dans l'EMAG ne sont pas toujours suffisants pour stabiliser le produit et ne permettent pas de lutter contre l'action des métaux (catalyseurs des phénomènes d'oxydation et de dégradation). Cette instabilité du carburant peut conduire à des phénomènes d'encrassement des filtres et systèmes d'injection.
• extraction des métaux : les EMAG et leurs sous-produits ont tendance à favoriser l'extraction des métaux avec qui ils sont mis en contact, par exemple matériaux de transport, stockage et/ ou pièces ou organes.
• tenue à froid : en particulier pour les gazoles non routier, étant donnée la duré de stockage prolongée de tels carburants qui est parfois supérieure à 6 mois, et compte tenu de la saisonnalité des spécifications en période hivernale ou intersaison, la tenue à froid peut s'avérer problématique pour l'utilisateur (problèmes de cristallisation, sédimentation, bouchage de filtres,...).

Non-road diesel of standard quality (currently compliant with EN 590) sometimes poses problems in terms of:

• storage stability and use: in case of prolonged storage or when used under conditions of pressure or high temperatures: the antioxidants incorporated in the EMAG are not always sufficient to stabilize the product and do not make it possible to fight against the action of metals (catalysts of oxidation and degradation phenomena). This instability of the fuel can lead to fouling phenomena of the filters and injection systems.
• Metals extraction: EMAGs and their by-products tend to favor the extraction of metals with which they come into contact, eg transport materials, storage and / or parts or organs.
• cold-held: especially for non-road diesel, given the extended storage period of such fuels, which is sometimes greater than 6 months, and taking into account the seasonality of the specifications in winter or inter-season, the cold resistance can be 'to prove problematic for the user (problems of crystallization, sedimentation, clogging of filters, ...).

The document US-A1-2003 / 0196372 discloses the use of a combination of an aromatic amine and a hindered phenol as an antioxidant. This document describes an additive composition suitable for lowering the deposits on the valves (Internal Valve Deposit). The additive composition comprises said combination: anti-oxidant, a metal deactivator (N, N'-bis-salicylidene-1,2-propane diamine) and a detergent (polyisobutylene diamine) (see paragraph [0028]).

CN 102,051,239 discloses a stabilized gas oil composition comprising a major portion of gas oil and a minor portion of an additive composition comprising a polyether amine, a metal inactivating agent, an antioxidant, a hindered alkylphenol, or a mixture of both.

There is therefore a need to improve the quality of gas oils and, in particular, to provide novel additive compositions capable of improving the properties of gas oils whatever their destination or their composition (with or without a product of renewable origin): diesel road or non-road diesel, type B0 to B7.

Presentation of the invention

The present invention provides a high quality road or off-road diesel which has improved properties compared to the corresponding standard-quality road or off-road diesel (EN 590). Within the meaning of the present invention, many of the properties of standard diesel are improved, and in particular the oxidation resistance, storage stability, thermal stability and engine performance (reduction of fouling of injectors; can also be improved: reduction of power loss; reduction of clogging tendency of filters. ...); cold holding (TLF and pour point).

The invention also relates to additive compositions capable of improving the properties of diesel, in particular non-road diesel such as oxidation resistance, storage stability, thermal stability, engine performance (reduction in clogging of the injectors); the cold behavior (TLF and pour point), the reduction of the power loss, the reduction of the clogging tendency of the filters ....) can also be improved.

This additive composition added to the fuel (road or non-road diesel) more particularly makes it possible to reduce the tendency of the injectors to become fouled by the fuel. Fouling injectors can lead to power losses but also a degradation of the combustion responsible for an increase in polluting emissions.

Brief description of the drawings

Other advantages and features will emerge more clearly from the following description of particular embodiments of the invention given as non-limiting examples and represented in the single accompanying drawing in which the figure 1 represents the loss of power (in%) as a function of the duration (in hours) of an injector fouling test according to the procedure CEC DW10 referenced SG-F-098, on a composition of diesel fuel, diesel G0 reference and a diesel diesel fuel composition G ₁ according to the present invention.

The invention is defined by the claims.

1. a) au moins un désactivateur de métaux ou agent chélatant,
2. b) au moins un anti-oxydant de type phénol encombré (alkylphénol),
3. c) au moins un agent dispersant,
   et éventuellement
4. d) au moins un neutralisateur d'acidité (acid scavenger en anglais) de type amine aliphatique, cycloaliphatique ou aromatique,
5. e) au moins un additif de tenue à froid,
6. f) au moins un traceur ou marqueur,
7. g) au moins un agent parfumant et/ou masquant d'odeur et/ou réodorant,
8. h) au moins un agent biocide,
9. i) au moins un passivateur de métaux.

A first subject of the invention relates to additive compositions comprising the following components:

1. a) at least one metal deactivator or chelating agent,
2. b) at least one hindered phenol type antioxidant (alkylphenol),
3. c) at least one dispersing agent,
   and eventually
4. d) at least one aliphatic, cycloaliphatic or aromatic amine acid scavenger (acid scavenger),
5. e) at least one cold-holding additive,
6. f) at least one tracer or marker,
7. g) at least one perfuming and / or odor-masking and / or re-odoring agent,
8. h) at least one biocidal agent,
9. i) at least one metal passivator.

• a) au moins un désactivateur de métaux ou agent chélatant,
• b) au moins un anti-oxydant de type phénol encombré (alkylphénol),
• c) au moins un agent dispersant,
• i) au moins un passivateur de métaux,
  et éventuellement
• d) au moins un neutralisateur d'acidité (acid scavenger en anglais) de type amine aliphatique, cycloaliphatique ou aromatique,
• e) au moins un additif de tenue à froid,
• f) au moins un traceur ou marqueur,
• g) au moins un agent parfumant et/ou masquant d'odeur et/ou réodorant,
• h) au moins un agent biocide.

According to a particular preferred embodiment, the additive compositions comprise the following components:

• a) at least one metal deactivator or chelating agent,
• b) at least one hindered phenol type antioxidant (alkylphenol),
• c) at least one dispersing agent,
• i) at least one metal passivator,
  and eventually
• d) at least one aliphatic, cycloaliphatic or aromatic amine acid scavenger (acid scavenger),
• e) at least one cold-holding additive,
• f) at least one tracer or marker,
• g) at least one perfuming and / or odor-masking and / or re-odoring agent,
• h) at least one biocidal agent.

The metal passivator i) is chosen from triazole derivatives, alone or as a mixture, for example benzotriazole derivatives. The term "triazole derivatives" means all the compounds comprising a triazole unit, that is to say a 5-membered aromatic ring unit, having two double bonds and 3 nitrogen atoms. Depending on the position of the nitrogen atoms, we distinguish the 1,2,3-triazole units (called V-triazoles) and the units 1,2,4-triazoles (called S-triazoles). As an example of triazole units, mention may be made of benzotriazole or tolyltriazole.

The metal passivator i) may be chosen from amines substituted with triazole groups, alone or as a mixture. The term "triazole group" means any substituent containing a triazole unit as defined above.

The metal passivator (s) i) may, for example, be chosen from N, N-Bis (2-ethylhexyl) -1,2,4-triazol-1-ylmethanamine (CAS 91273-04-0) and N, N'-bis- (2-ethylhexyl) -4-methyl-1H-benzotriazole amine (CAS80584-90-3), alone or in admixture and the passivators described on page 5 of US2006 / 0272597 cited as an example.

In particular, the metal passivator is advantageously chosen from N, N-Bis (2-ethylhexyl) -1,2,4-triazol-1-ylmethanamine (CAS 91273-04-0) and N, N ' -bis- (2-ethylhexyl) -4-methyl-1H-benzotriazole amine (CAS80584-90-3), alone or in admixture.

Depending on the nature and miscibility of constituents a) to i) of the additive composition according to the invention, with the gas oil, the additive composition may also contain one or more hydrocarbon organic solvents and optionally at least one compatibilizing agent or cosolvent.

Preferably, the additive composition further comprises at least one hydrocarbon organic solvent and / or at least one compatibilizer or co-solvent.

The metal deactivator (s) or chelating agent (a) may be chosen from amines substituted with N, N'-disalicylidene groups, such as N, N'-disalicylidene 1,2-diaminopropane (DMD).

The antioxidant agent (s) b) may be chosen from molecules comprising at least one hindered phenol group (alkylphenols), alone or in mixed ; examples of hindered phenol type antioxidants include 2,6-di-tert-butyl-4-methyl-phenol (BHT), t-butyl hydroquinone (TBHQ), 2,6 and 2,4-tert-butyl phenol, 2,4-dimethyl-6-t-butyl phenol, pyrogallol, todopherol, 4,4'-methylene bis (2,6-di-t-butyl phenol) ) (CAS RN 118-82-1), alone or in mixture.

• ∘ les amines substituées telle que la N-polyisobutèrie amine R1-NH₂, la N-polyisobutènethylènediamine R1-NH-R2-NH₂, ou encore les polysiobutènesuccinimides de formule
  
  où R₁ représente un groupement polyisobutène de masse moléculaire compris entre 140 et 5000 et de préférence entre 500 et 2000 ou, de préférence, entre 750 et 1250 ;
  R₂ représente au moins l'un des segments suivants -CH₂-CH₂-, CH₂-CH₂-CH₂, -CH-CH(CH₃)-
  et x un nombre entier compris entre 1 et 6.

The dispersant (s) c) may for example be chosen from:

• Substituted amines such as amine N-polyisobutylene amine R 1 -NH ₂ , N-polyisobutenyl ethylene diamine R ₁ -NH-R ₂ -NH ₂ , or alternatively polysiobutenyl succinimides of formula
  
  where R ₁ represents a polyisobutene group of molecular mass between 140 and 5000 and preferably between 500 and 2000 or, preferably, between 750 and 1250;
  R ₂ represents at least one of the following segments -CH ₂ -CH ₂ -, CH ₂ -CH ₂ -CH ₂ , -CH-CH (CH ₃ ) -
  and x an integer from 1 to 6.

• ∘ les polyétheramines de formule :
  
  où :
  • R est un groupement alkyle comportant de 1 to 30 atomes de carbone;
  • R1 et R2 sont chacun indépendamment un atome d'hydrogène, une chaîne alkyle de 1 à 6 atomes de carbone ou -O-CHR1-CHR2- ;
  • A est une amine ou N-alkylamine avec 1 à 20 atomes de carbone dans la chaîne alkyle, une N,N-dialkylamine ayant de 1 à 20 atomes de carbone dans chaque groupe alkyle, ou une polyamine avec 2 à 12 atomes d'azote et de 2 à 40 atomes de carbone.
  • et x allant de 5 à 100;

Polyethyleneamines are particularly effective. They are for example described in detail in the reference "Ethylene Amines" Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950) ).

• ∘ polyetheramines of formula:
  
  or :
  • R is an alkyl group having 1 to 30 carbon atoms;
  • R1 and R2 are each independently hydrogen, an alkyl chain of 1 to 6 carbon atoms or -O-CHR1-CHR2-;
  • A is an amine or N-alkylamine with 1 to 20 carbon atoms in the alkyl chain, an N, N-dialkylamine having 1 to 20 carbon atoms in each alkyl group, or a polyamine with 2 to 12 nitrogen atoms and from 2 to 40 carbon atoms.
  • and x ranging from 5 to 100;

• ∘ les produits de réaction entre un phénol substitué par une chaîne hydrocarbonée un aldéhyde et une amine ou polyamine ou de l'ammoniac. Le groupement alkyle du phénol alkylé peut être constitué de 10 à 110 atomes de carbone. Ce groupement alkyle peut être obtenu par polymérisation de monomère oléfinique contenant de 1 à 10 atomes de carbone (éthylène ; propylène ; 1-butène, isobutylène et 1 décène). Les polyoléfines particulièrement utilisées sont le polyisobutène et/ou le polypropylène. Les polyoléfines ont en général une masse moléculaire moyenne en masse Mw comprise entre 140 et 5000 et de préférence entre 500 et 2000 ou de préférence entre 750 et 1250.

Such polyetheramines are for example marketed by the companies BASF, HUNSTMAN or CHEVRON.

• ∘ reaction products between a phenol substituted by a hydrocarbon chain an aldehyde and an amine or polyamine or ammonia. The alkyl group of the alkylated phenol may be from 10 to 110 carbon atoms. This alkyl group can be obtained by polymerization of olefinic monomer containing from 1 to 10 carbon atoms (ethylene, propylene, 1-butene, isobutylene and 1 decene). The polyolefins particularly used are polyisobutene and / or polypropylene. The polyolefins generally have a weight average molecular weight Mw of between 140 and 5000 and preferably between 500 and 2000 or preferably between 750 and 1250.

The alkyl phenols can be prepared by alkylation reaction between a phenol and an olefin or a polyolefin such as polyisobutylene or polypropylene. The aldehyde used may contain from 1 to 10 carbon atoms, usually formaldehyde or paraformaldehyde.

• ∘ les autres dispersants, tels que :
  • les dispersants carboxyliques comme ceux décrits dans US 3,219,666 ;
  • les dispersants aminés issus de la réaction entre des aliphatiques halogénés de haut poids moléculaire avec des amines ou des polyamines de préférence des polyalkylène polyamines, décrits par exemple dans US 3 565 804 ;
  • les dispersants polymériques obtenus par polymérisation d'alkylacrylates ou alkylméthacrylates (chaînes alkyles en C8 à C30), des aminoalkylacrylates ou acrylamides et des acrylates substitués par des groupements poly-(oxyéthylène). Des exemples de dispersants polymériques sont par exemple décrits dans US 3 329 658 et US 3 702 300 .

The amine used may be an amine or a polyamine including alkanol amines having one or more hydroxy groups. The amines used are in general chosen from ethanolamine, diethanolamines, methylamine, dimethylamine, ethylenediamine, dimethylaminopropylamine, diethylenetriamine and / or 2- (2-aminoethylamino) ethanol. This dispersant can be prepared by a Mannich reaction by reacting an alkylphenol, an aldehyde and an amine as described in US Patent 5,697,988 .

• ∘ other dispersants, such as:
  • carboxylic dispersants such as those described in US 3,219,666 ;
  • the aminated dispersants derived from the reaction between halogenated aliphatics of high molecular weight with amines or polyamines, preferably polyalkylene polyamines, described for example in US 3,565,804 ;
  • polymeric dispersants obtained by polymerization of alkylacrylates or alkylmethacrylates (C8-C30 alkyl chains), aminoalkylacrylates or acrylamides and acrylates substituted with poly (oxyethylene) groups. Examples of polymeric dispersants are for example described in US 3,329,658 and US 3,702,300 .

The possible neutralizer or acid scavenger (d) may be chosen from aliphatic, cycloaliphatic and aromatic amines. In a preferred manner, dimethylcyclohexylamine is preferably used as acid neutralizer.

The cold-holding additive (s) e) may be chosen from pour point-improving additives (for point), additives improving the filterability limit temperature (TLF), additives improving the cloud point (cloud point). and / or anti-settling and / or dispersing paraffin additives.

As examples of additives improving the pour point and the filterability (CFI), mention may be made of copolymers of ethylene and vinyl acetate (EVA) and / or copolymers of ethylene and propionate of vinyl (EVP).

By way of examples of additives improving the TLF, mention may be made of the polyfunctional cold operability additives chosen in particular from the group consisting of olefin and alkenyl nitrate polymers such as those described in US Pat. EP 573,490 .

By way of examples of cloud point-improving additives, mention may be made in a nonlimiting manner of the compounds chosen from the group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide ester and ester polymers. of fumaric / maleic acids. Examples of such additives are given in EP 71,513 , EP 100 248 , FR 2 528 051 , FR 2 528 051 , FR 2,528,423 , EP1 12,195 , EP 1 727 58 , EP 271,385 , EP 291367 .

By way of examples of anti-sedimentation and / or paraffin dispersant additives, anti-sedimentation additives (but not limited to) selected from the group consisting of (meth) acrylic acid / (meth) copolymers may be used in particular. polyamine amidated alkyl acrylate, polyamine alkenyl succinimides, phthalamic acid and double chain fatty amine derivatives; alkyl phenol / aldehyde resins; examples of such additives are given in EP 261 959 , EP593 331 , EP 674 689 , EP 327 423 , EP 512,889 , EP 832 172 ; US 2005/0223631 ; US 5,998,530 ; WO 93/14178 .

Preferably, the additive compositions according to the invention contain ethylene / vinyl acetate copolymers (EVA) and / or ethylene / vinyl acetate / vinyl versatate terpolymers (VEOVA) and / or ethylene / vinyl acetate terpolymers. / acrylate ester (2-ethylhexyl acrylate) as a cold-holding additive e)

• ▪ 3a,4,5,6,7,7a-hexahydro-4,7-methano-1 h-inden-5 (ou 6) -yl isobutyrate (CAS 67634-20-2)
• ▪ tricyclodécényl propionate (CAS 17511-60-3)
• ▪ acétate de cis 3 hexenyle (CAS 3681-71-8)
• ▪ éthyl linalol (CAS 10339-55-6)
• ▪ acétate de prényle (CAS 1191-16-8)
• ▪ myristate d'éthyle (CAS 124-06-1)
• ▪ acétate de para tertio butyl cyclo hexyl (CAS 32210-23-4)
• ▪ acétate de butyle (CAS 123-86-4),
• ▪ 4,7-méthano-1h-inden-6-ol, 3a,4,5,6,7,7a-hexahydro-, acétate (CAS 5413-60-5)
• ▪ caprate d'éthyle (CAS 110-38-3)

The optional marker (s) f) may be chosen in particular from the following aliphatic or cycloaliphatic esters:

• 3a, 4,5,6,7,7a-hexahydro-4,7-methano-1h-inden-5 (or 6) -yl isobutyrate (CAS 67634-20-2)
• Tricyclodecenyl propionate (CAS 17511-60-3)
• ▪ cis 3 hexenyl acetate (CAS 3681-71-8)
• ▪ ethyl linalool (CAS 10339-55-6)
• ▪ prenyl acetate (CAS 1191-16-8)
• ▪ ethyl myristate (CAS 124-06-1)
• ▪ para tertio butyl cyclohexyl acetate (CAS 32210-23-4)
• ▪ Butyl acetate (CAS 123-86-4),
• ▪ 4,7-methano-1h-inden-6-ol, 3a, 4,5,6,7,7a-hexahydro-, acetate (CAS 5413-60-5)
• ▪ ethyl caprate (CAS 110-38-3)

• * les composés tricycliques organiques décrits dans EP 1.591.514 qui sont des composés tricycliques organiques de formule (I) ci-après
  
  dans laquelle le cycle cyclopentane est saturé ou insaturé, et R1, R2, R3, identiques ou différents, sont choisis parmi l'hydrogène et les radicaux hydrocarbonés comprenant de 1 à 10 atomes de carbone et comportant éventuellement un ou plusieurs hétéroatomes ainsi que
• * les aldéhydes aliphatiques ou aromatiques tels que la vanilline,
• * les esters aliphatiques ou aromatiques, tels que l'acétate de benzyle,
• * les alcools, tels que le linalol, les alcools phényléthyliques,
• * les cétones, telles que le camphre cristallisé, l'éthylmaltol,
• * les huiles essentielles, telles que l'huile essentielle dérivées d'agrumes seuls ou en mélanges.

The perfume and / or odor masking agent (s) and / or odor remover (s) g) may be chosen from:

• * the organic tricyclic compounds described in EP 1.591.514 which are organic tricyclic compounds of formula (I) below
  
  in which the cyclopentane ring is saturated or unsaturated, and R1, R2, R3, which are identical or different, are chosen from hydrogen and hydrocarbon radicals comprising from 1 to 10 carbon atoms and optionally containing one or more heteroatoms, and
• aliphatic or aromatic aldehydes such as vanillin,
• aliphatic or aromatic esters, such as benzyl acetate,
• alcohols, such as linalool, phenylethyl alcohols,
• ketones, such as crystallized camphor, ethylmaltol,
• * essential oils, such as essential oil derived from citrus alone or in mixtures.

Advantageously, a mixture of at least one organic tricyclic compound and at least one aldehyde, an ester, a hydroxide, a ketone, an essential oil, is preferably used as scenting, odor masking or reodorant agent g). as defined above.

• les oxazolidines : 3,3'-méthylènebis[5-méthyloxazolidine] (CAS N°66204-44-2) ;
• les mélanges (CAS N° 55965849) des composés suivants : 5-chloro-2-methyl-2H-isothiazol-3-one (CAS : 26172-55-4 et EINECS 247-500-7) et 2-méthyl-2H-isothiazol-3-one (CAS N°2682-20-4 et EINECS 220-239-6) ;
• les mélanges d'isothiocyanates : méthylène bis(thiocyanate) (CAS : 6317-18-6) et 2-(thiocyano methylthio)benzothiazole (CAS : 21564-17-0) ;
• les sels d'ammonium quaternaires sous forme de chlorures obtenus à partir d'alkyl benzène en C12-C18 ou d'alkyl diméthyl benzène.

The biocidal agent (s) h) can be chosen from:

• oxazolidines: 3,3'-methylenebis [5-methyloxazolidine] (CAS No. 66204-44-2);
• mixtures (CAS No. 55965849) of the following compounds: 5-chloro-2-methyl-2H-isothiazol-3-one (CAS: 26172-55-4 and EINECS 247-500-7) and 2-methyl-2H- isothiazol-3-one (CAS No. 2682-20-4 and EINECS 220-239-6);
• mixtures of isothiocyanates: methylene bis (thiocyanate) (CAS: 6317-18-6) and 2- (thiocyano methylthio) benzothiazole (CAS: 21564-17-0);
• quaternary ammonium salts in the form of chlorides obtained from C12-C18 alkyl benzene or from alkyl dimethyl benzene.

Some of the components of the compositions according to the invention may have several functionalities, typically marker and perfuming agent: a component may be both a marker and a perfuming agent.

1. a) au moins un séquestrant de métaux choisi parmi les amines substituées par des groupements N,N'-disalicylidène, tels que N,N'-disalicylidène 1,2-diaminopropane (DMD),
2. b) au moins un agent anti-oxydant de type phénol encombré, choisi parmi les molécules comprenant au moins un groupe phénol encombré, seules ou en mélange ; à titre d'exemple d'anti-oxydant de type phénol encombré, on peut citer le di-t-butyl-2,6 méthyl-4 phénol (BHT), la t-butyl hydroquinone (TBHQ), le 2,6 ou le 2,4 di-t-butyl phénol, le 2,4-diméthyl-6- t-butyl phénol, le pyrogallol, le tocophérol, le 4,4'- méthylène bis (2,6-di-t-butyl phénol) (N° CAS 118-82-1), seuls ou en mélange,
3. c) au moins un agent dispersant et/ou détergent, choisi de préférence parmi les PIBSI,
4. d) au moins un neutralisateur d'acidité de type amine, et éventuellement
5. e) au moins un additif améliorant la tenue à froid choisi parmi les copolymères EVA et/ou terpolymères VEOVA,
6. f) au moins un marqueur ou traceur,
7. g) au moins un agent parfumant et/ou masquant d'odeur et/ou réodoraht, choisi parmi:
   • * les composés tricycliques organiques décrits dans EP 1.591.514 qui sont des composés tricycliques organiques de formule (I) ci-après
     
     dans laquelle le cycle cyclopentane est saturé ou insaturé, et R1, R2, R3, identiques ou différents, sont choisis parmi l'hydrogène et les radicaux hydrocarbonés comprenant de 1 à 10 atomes de carbone et comportant éventuellement un ou plusieurs hétéroatomes
     ainsi que
   • * les aldéhydes aliphatiques ou aromatiques tels que la vanilline,
   • * les esters aliphatiques ou aromatiques, tels que l'acétate de benzyle,
   • * les alcools, tels que le linalol, les alcools phényléthyliques,
   • * les cétones, telles que le camphre cristallisé, l'éthyrmaltol,
   • * les huiles essentielles, telles que l'huile essentielle dérivée d'agrumes
   • * leurs mélanges,
     et de préférence, le mélange d'au moins un composé tricyclique organique et d'au moins un aldéhyde, un ester, un hydroxyde, une cétone, une huile essentielles, et/ou
8. h) au moins un additif biocide,
9. i) au moins un passivateur de métaux i) choisi parmi les amines substituées par des groupements triazole, tels que benzotriazole, toluyltriazole.

Preferably, the additive composition according to the invention comprises:

1. a) at least one metal sequestrant chosen from amines substituted with N, N'-disalicylidene groups, such as N, N'-disalicylidene 1,2-diaminopropane (DMD),
2. b) at least one hindered phenol type antioxidant, chosen from molecules comprising at least one hindered phenol group, alone or as a mixture; as an example of a hindered phenol type antioxidant, there may be mentioned 2,6-di-tert-butyl-4-methylphenol (BHT), tert-butyl hydroquinone (TBHQ), 2,6 or 2,4-tert-butyl phenol, 2,4-dimethyl-6-t-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene bis (2,6-di-t-butyl phenol) ) (CAS RN 118-82-1), singly or in combination,
3. c) at least one dispersing agent and / or detergent, preferably selected from PIBSI,
4. d) at least one amine neutralization neutralizer, and optionally
5. e) at least one additive improving the cold resistance chosen from the EVA copolymers and / or terpolymers VEOVA,
6. f) at least one marker or tracer,
7. g) at least one perfuming and / or masking odor and / or reodoraht agent chosen from:
   • * the organic tricyclic compounds described in EP 1.591.514 which are organic tricyclic compounds of formula (I) below
     
     in which the cyclopentane ring is saturated or unsaturated, and R1, R2, R3, which are identical or different, are chosen from hydrogen and hydrocarbon radicals comprising from 1 to 10 carbon atoms and optionally comprising one or more heteroatoms
     as well as
   • aliphatic or aromatic aldehydes such as vanillin,
   • aliphatic or aromatic esters, such as benzyl acetate,
   • alcohols, such as linalool, phenylethyl alcohols,
   • ketones, such as crystalline camphor, ethyrmaltol,
   • * essential oils, such as essential oil derived from citrus fruits
   • * their mixtures,
     and preferably, the mixture of at least one organic tricyclic compound and at least one essential aldehyde, ester, hydroxide, ketone, oil, and / or
8. h) at least one biocidal additive,
9. i) at least one metal passivator i) selected from amines substituted with triazole groups, such as benzotriazole, toluyltriazole.

• a) au moins un séquestrant de métaux choisi parmi les amines substituées par des groupements N,N'-disalicylidène, tels que N,N'-disalicylidène 1,2-diaminopropane (DMD),
• b) au moins un agent anti-oxydant de type phénol encombré, choisi parmi les molécules comprenant au moins un groupe phénol encombré, seules ou en mélange ; à titre d'exemple d'anti-oxydant de type phénol encombré, on peut citer le di-t-butyl-2,6 méthyl-4 phénol (BHT), la t-butyl hydroquinone (TBHQ), le 2,6 ou le 2,4 di-t-butyl phénol, le 2,4'-diméthyl-6- t-butyl phénol, le pyrogallol, le tocophérol, le 4,4'- méthylène bis (2,6-di-t-butyl phénol) (N° CAS 118-82-1), seuls ou en mélange, et d'une manière générale parmi les molécules ,
• c) au moins un agent dispersant et/ou détergent, choisi de préférence parmi les PIBSI,
• d) au moins un neutralisateur d'acidité de type amine,
• i) au moins un passivateur de métaux i) choisi parmi les amines substituées par des groupements triazole, tels que benzotriazole, toluyltriazole,
  et éventuellement
• e) au moins un additif améliorant la tenue à froid choisi parmi les copolymères EVA et/ou terpolymères VEOVA,
• f) au moins un marqueur ou traceur,
• h) au moins un additif biocide, et/ou
• g) au moins un agent parfumant et/ou masquant d'odeur et/ou réodorant, choisi parmi :
  • * les composés tricycliques organiques décrits dans EP 1.591.514 qui sont des composés tricycliques organiques de formule (I) ci-après
    
    dans laquelle le cycle cyclopentane est saturé ou insaturé, et R1, R2, R3, identiques ou différents, sont choisis parmi l'hydrogène et les radicaux hydrocarbonés comprenant de 1 à 10 atomes de carbone et comportant éventuellement un ou plusieurs hétéroatomes
    ainsi que
  • * les aldéhydes aliphatiques ou aromatiques tels que la vanilline,
  • * les esters aliphatiques ou aromatiques, tels que l'acétate de benzyle,
  • * les alcools, tels que le linalol, les alcools phényléthyliques,
  • * les cétones, telles que le camphre cristallisé, l'éthylmaltol,
  • * les huiles essentielles, telles que l'huile essentielle dérivée d'agrumes
  • * leurs mélanges,

et de préférence, le mélange d'au moins un composé tricyclique organique et d'au moins un aldéhyde, un ester, un hydroxyde, une cétone, une huile essentielle.According to a particular preferred embodiment, the additive composition according to the invention comprises:

• a) at least one metal sequestrant chosen from amines substituted with N, N'-disalicylidene groups, such as N, N'-disalicylidene 1,2-diaminopropane (DMD),
• b) at least one hindered phenol type antioxidant, chosen from molecules comprising at least one hindered phenol group, alone or as a mixture; as an example of a hindered phenol type antioxidant, there may be mentioned 2,6-di-tert-butyl-4-methylphenol (BHT), tert-butyl hydroquinone (TBHQ), 2,6 or 2,4-tert-butyl phenol, 2,4'-dimethyl-6-t-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene bis (2,6-di-t-butyl) phenol) (CAS No. 118-82-1), alone or as a mixture, and generally among the molecules,
• c) at least one dispersing agent and / or detergent, preferably selected from PIBSI,
• d) at least one amine neutralization neutralizer,
• i) at least one metal passivator i) chosen from amines substituted with triazole groups, such as benzotriazole, toluyltriazole,
  and eventually
• e) at least one additive improving the cold resistance chosen from the EVA copolymers and / or terpolymers VEOVA,
• f) at least one marker or tracer,
• h) at least one biocidal additive, and / or
• g) at least one scenting and / or odor masking and / or re-odoring agent chosen from:
  • * the organic tricyclic compounds described in EP 1.591.514 which are organic tricyclic compounds of formula (I) below
    
    in which the cyclopentane ring is saturated or unsaturated, and R1, R2, R3, which are identical or different, are chosen from hydrogen and hydrocarbon radicals comprising from 1 to 10 carbon atoms and optionally comprising one or more heteroatoms
    as well as
  • aliphatic or aromatic aldehydes such as vanillin,
  • aliphatic or aromatic esters, such as benzyl acetate,
  • alcohols, such as linalool, phenylethyl alcohols,
  • ketones, such as crystallized camphor, ethylmaltol,
  • * essential oils, such as essential oil derived from citrus fruits
  • * their mixtures,

and preferably, the mixture of at least one organic tricyclic compound and at least one aldehyde, an ester, a hydroxide, a ketone, an essential oil.

In addition to the components described above, the additive composition according to the invention may contain, in addition to the additive (s) according to the invention, one or more other additives, different from the constituents a) to i), and the solvent (s) and / or or co-solvents such as for example other markers than those corresponding to the definition of the markers e) and in particular the markers imposed by the regulation, for example the Red dye, which is currently the regulatory color of non-road diesel and fuel oil domestic, demulsifiers; anti-static additives or conductivity improvers; lubricant additives, anti-wear agents and / or friction modifiers, the additives improving combustion including cetane-enhancing additives, anti-foam additives ...

• de 0,1 à 5 % masse et de préférence de 1 à 2 % masse de séquestrant(s) de métaux a),
• de 1 à 30 % masse et de préférence de 2,5 à 10 % masse d'agent(s) anti-oxydant(s) de type phénol encombré (alkylphénol) b),
• de 0,5 à 20 % masse et de préférence de 1 à 10 % masse d'agent(s) dispersant(s) et/ou détergent(s) c),
• de 0 à 20 % masse, de préférence de 0,5 à 20 % masse et avantageusement de 1 à 10 % masse de neutralisateurs d'acidité d),
• de 0 à 30 % masse et de préférence de 10 à 20 % masse d'additif(s) de tenue à froid e),
• de 0 à 5 % masse et de préférence de 0,2 à 5 % masse de traceur(s) f),
• de 0 à 10 % masse et de préférence de 2 à 5 % masse d'agent(s) parfumant(s) et/ou masquant(s) d'odeur et/ou réodorant(s) g),
• de 0 à 20 % masse et de préférence de 5 à 10 % masse et avantageusement de 1 à 2% masse d'agent(s) biocide(s) h),
• de 0 à 5 % masse ou jusqu'à 5% masse, de préférence de 0,1 à 5%, plus préférentiellement de 0,5 à 3,5%, encore plus préférentiellement de 1 à 2% en masse de passivateur(s) de métaux i),
• de 10 à 80 % masse et de préférence de 20 à 50 % masse de solvant(s) organique(s) hydrocarboné(s),
• de 10 à 60 % masse et de préférence de 20 à 40 % masse d'agent(s) compatibilisant(s) ou co-solvant(s).

Preferably, the additive compositions according to the invention comprise:

• from 0.1 to 5% by weight and preferably from 1 to 2% by weight of metal sequestrant (s) a),
• from 1 to 30% by weight and preferably from 2.5 to 10% by mass of hindered phenol (alkylphenol) b) antioxidant agent (s),
• from 0.5 to 20% by weight and preferably from 1 to 10% by mass of dispersing agent (s) and / or detergent (s) c),
• from 0 to 20% by weight, preferably from 0.5 to 20% by weight and advantageously from 1 to 10% by mass of acid neutralizers d),
• from 0 to 30% by weight and preferably from 10 to 20% by weight of cold-holding additive (s) e),
• from 0 to 5% by weight and preferably from 0.2 to 5% by mass of tracer (s) f),
• from 0 to 10% by weight and preferably from 2 to 5% by weight of perfume agent (s) and / or odor masking (s) and / or deodorant (s) g),
• from 0 to 20% by weight and preferably from 5 to 10% by weight and advantageously from 1 to 2% by mass of biocidal agent (s) h),
• from 0 to 5% by weight or up to 5% by mass, preferably from 0.1 to 5%, more preferably from 0.5 to 3.5%, even more preferably from 1 to 2% by weight of passivator (s). ) of metals i),
• from 10 to 80% by weight and preferably from 20 to 50% by weight of organic hydrocarbon solvent (s),
• from 10 to 60% by weight and preferably from 20 to 40% by weight of compatibilizing agent (s) or co-solvent (s).

According to a second subject, the invention relates to a method for preparing the additive compositions as defined above, by mixing, preferably at ambient temperature, components a) to c), and optionally e) to i) said compositions and / or solvent (s) and / or compatibilizing agents, in one or more steps according to any suitable mixing means.

According to a particular embodiment, the process for preparing the additive compositions as defined above is carried out by mixing, preferably at ambient temperature, components a) to c) and compound i), and optionally e) h) said compositions and / or solvent (s) and / or compatibilizing agents, in one or more steps according to any suitable mixing means.

When the additive compositions according to the invention also comprise solvent (s) and / or co-solvent, they can be prepared in the same way, by mixing the components in one or more steps.

The additive compositions according to the invention have the additional advantage of being storage stable for at least several months at temperatures generally ranging from -15 ° C. to + 40 ° C. and can therefore be stored, for example in deposit, in refinery, before mixing with standard diesel or non-road diesel.

• une majeure partie d'un mélange à base d'hydrocarbures liquides ayant des températures de distillation comprises entre 150 à 380°C, de préférence entre 160 et 370°C, plus préférentiellement entre 180 et 370°C. Ces mélanges sont en général issus de coupes de types distillats moyens, issues de raffineries et/ou d'agrocarburants et/ou de biocarburants et/ou de biomasse et/ou de carburants de synthèse, et notamment de coupes kérosène en général riches en composés aromatiques (benzène, ...)
• une mineure partie comprenant au moins une composition d'additifs telle que définie ci-dessus, et éventuellement un ou plusieurs autres additifs que ceux de la ou des compositions d'additifs selon l'invention, qui peuvent ou non être sous forme de paquet d'additifs.

According to a third object the invention relates to a liquid fuel composition of diesel type comprising:

• a major part of a mixture based on liquid hydrocarbons having distillation temperatures of between 150 to 380 ° C, preferably between 160 and 370 ° C, more preferably between 180 and 370 ° C. These mixtures are generally derived from cuts of the middle distillate type, from refineries and / or agrofuels and / or biofuels and / or biomass and / or synthetic fuels, and in particular kerosene cuts in general rich in compounds. aromatic (benzene, ...)
• a minor portion comprising at least one additive composition as defined above, and optionally one or more other additives than those of the or additive compositions according to the invention, which may or may not be in the form of an additive package.

"Fuel" is a fuel that supplies an internal combustion engine. In particular, a diesel type liquid fuel is considered as a fuel that feeds a Diesel type engine.

By "major part" it is meant that the diesel type liquid fuel composition comprises at least 50% by weight of the liquid hydrocarbon mixture.

The mixture based on liquid hydrocarbons is advantageously constituted by any mixture of hydrocarbons that can be used as diesel fuel. Diesel fuels generally comprise hydrocarbon cuts having a distillation range (determined according to ASTM D 86) between 150 and 380 ° C, with an initial point between 150 and 180 ° C and an end point between 340 and 380 ° C. The density at 15 ° C of gas oils is typically between 0.810 and 0.860.

According to a particular embodiment, the diesel type liquid fuel composition may comprise a product of renewable origin such as fatty acid esters. The renewable product content of the diesel fuel liquid fuel composition is advantageously at least 0.2% by weight. The diesel fuel liquid fuel composition may comprise at least seven parts by volume of at least one product of renewable origin. The product of renewable origin is chosen from esters of fatty acids, essentially or exclusively of animal or vegetable origin. The fatty acid esters are advantageously fatty acid methyl esters (FAMEs), which are essentially or exclusively of plant or animal origin, for example esters of vegetable and / or animal oils, in particular methyl esters of vegetable oils or FAME.

Preferably, the liquid fuel composition of the diesel road or non-road type according to the invention comprises from 100 to 2000 ppm, preferably from 250 to 1500 ppm, more preferably from 250 to 1000 ppm by weight of composition (s) of additives such as (s) as defined above.

Any other additives are generally incorporated in amounts ranging from 50 to 1500 ppm by weight.

By way of examples of any other additives, mention may be made, without limitation, of lubricant or anti-wear additives, combustion improvers, anti-foam agents, anti-corrosion agents, detergents, etc.

The diesel fuel type liquid fuel compositions according to the invention may be prepared by mixing the liquid fuel, the additive composition or compositions according to the invention and the optional additive (s), in one or more stages, generally at ambient temperature. It is not beyond the scope of the invention to separately mix the components of the additive composition according to the invention (additives a) to c)), optionally additives d) to i), the solvent (s) ( s) and / or co-solvent (s)), any other additives (in pack form or not) with the diesel type fuel.

According to a fourth subject, the invention relates to the use of the additive compositions as described above as an agent improving the storage stability, the oxidation resistance, the cold resistance and, more particularly, the engine performance. in particular the reduction of fouling (clogging and clogging) of diesel fuels, in particular non-road diesel fuels.

The invention also relates to the use of the liquid fuel compositions based on diesel fuel according to the invention as defined above as diesel fuel of higher quality, ie having stability properties. storage and vis-à-vis materials, resistance to oxidation, cold resistance and, more particularly, engine performance including a reduction of fouling (fouling and clogging) higher than that of a diesel road and off-road standard quality (which meets at least the specifications of EN 590).

• * les engins mobiles non routiers, tels que
  • équipements de construction, notamment bulldozers, camions tout terrain, excavateurs tracteurs et chargeuses,
  • équipements d'entretien des routes
  • chasse-neige et balayeuses urbaines,
  • machines agricoles automotrices, équipements de sylviculture,
  • équipements de manutention, grues mobiles, chariots élévateurs,
  • échelles et nacelles automotrices,
  • équipements d'assistance aéroportuaire au sol
  • équipements industriels de forage,
  • compresseurs et motopompes,
  • locomotives ferroviaires,
  • groupes électrogènes ou hydrauliques sur camion,
• * les tracteurs agricoles ou forestiers,
• * les bateaux de plaisance,
• * les bateaux de navigation intérieure.

The diesel fuel of higher quality according to the invention, ie additive with at least one additive composition according to the invention, can be advantageously used as a fuel for the engines of non-road equipment listed in the Decree of 10/12/10, to know

• * non-road mobile machinery, such as
  • construction equipment, including bulldozers, off-road trucks, tractor and loader excavators,
  • road maintenance equipment
  • snow plow and street sweepers,
  • self-propelled agricultural machinery, forestry equipment,
  • handling equipment, mobile cranes, forklifts,
  • ladders and self-propelled platforms,
  • airport ground support equipment
  • industrial drilling equipment,
  • compressors and motor pumps,
  • railway locomotives,
  • truck-mounted generators or hydraulic generators,
• * agricultural or forestry tractors,
• * pleasure boats,
• * Inland navigation vessels.

Examples In Tables 1 and 2 below, the characteristics of non-road diesel in compliance with the Decree of 10 December 2010, that is non-road diesel of standard quality, are listed. <b> Table 1 </ b>: Characteristics of non-road diesel (Decree of December 10, 2010) PROPERTIES UNIT LIMITS mini Maxi Cetane number measured 51.0 Calculated cetane number 45.0 Density (at 15 ° C) kg / m ² 820 845 Polycyclic aromatic hydrocarbons % (m / m) - 8.0 Flash point ° C > 55 - Carbon residue (on the residue 10% distillation) % (M / m) - 0.30 Ash content % (M / m) - 0.01 Water content mg / kg - 200 Total contamination mg / kg - 24 Corrosion on the copper strip (3 h at 50 ° C) Quote Class 1 Oxidation stability 1: g / m ² - 25 h 20 - Oxidation stability 2: mg - 0.30 Variation of the acid number KOH / g Lubricating power corrected wear mark diameter microns - 460 (wsd 1.4) at 60 ° C Viscosity at 40% mm ² / s 2.00 4.50 Distillation: -% (v / v) condensed at 250 ° C: % (v / v) - 65 -% (v / v) condensed at 350 ° C: % (v / v) 85 - -point 95% (VN) condensed to: ° C - 360 Fatty acid esters content in accordance with the decree of the % (VN) - 7.0 ** ** 2010 relating to the characteristics of methyl esters of fatty acids SEASON DATED CLASSROOM TLF (° C max) Summer April ¹ - October 31 B 0 ° C Winter November 1 ^st - March 31 ^st E -15 ° C Non-road diesel F -20 ° C TLF: filterability limit temperature

Example 1 Preparation of Additive Compositions F1 to F5

• N,N'-disalicylidène 1,2-diaminopropane (séquestrant de métaux a)
• BHT (anti-oxydant de type alkylphénol) b)
• PIBSI (agent dispersant c))
• dicyclohexylamine (neutralisateur d)
• solvant aromatique (mélange de Solvarex 10 et 10 LN
• mélange 50/50 en poids de copolymère EVA et terpolymère VEOVA en solution dans du solvant aromatique (additif de TLF e))
• benzotriazole (passivateur de métaux i))

Tableau 3 Composants (% masse) a) séquestrant b) antioxydant d) neutralisateur c) dispersant i) passivateur e) TLF Solvant F1 1 5 0 0 0 14 80 F2 0 10 0 0 1 14 75 F3 1,5 4,5 0,75 1,5 1,5 14 76,25 F4 1 2,25 1,5 1,5 0 14 79,75 F5 1 3 0,5 1 1 14 79,5 Several additive compositions are prepared by mixing at room temperature several of the components listed below in proportions summarized in Table 3.

• N, N'-disalicylidene 1,2-diaminopropane (metal sequestering a)
• BHT (anti-oxidant alkylphenol type) b)
• PIBSI (dispersant agent c)
• dicyclohexylamine (neutralizer d)
• aromatic solvent (mixture of Solvarex 10 and 10 LN
• 50/50 mixture by weight of EVA copolymer and VEOVA terpolymer in solution in aromatic solvent (additive of TLF e))
• benzotriazole (metal passivator i))

<b> Table 3 </ b> Components (% mass) a) sequestering b) antioxidant d) neutralizer c) dispersant i) passivator e) TLF Solvent F1 1 5 0 0 0 14 80 F2 0 10 0 0 1 14 75 F3 1.5 4.5 0.75 1.5 1.5 14 76.25 F4 1 2.25 1.5 1.5 0 14 79.75 F5 1 3 0.5 1 1 14 79.5

• chaque composition d'additifs pure est placée dans une fiole tronconique en verre transparent qui est laissée fermée à une température constante choisie ; la composition testée est considérée comme stable et homogène à la température choisie si elle ne présente pas au-delà de 10 jours à ladite température, soit de phase démixée liquide dont la proportion serait supérieure à 0,5% de son volume, soit de sédiment ou dépôt solide supérieur à 0,05% de son volume. Des essais de stabilité ont été réalisés à deux températures différentes :
• - à la température du laboratoire (environ 20 °C) qui correspond aux conditions standard du test
• - à -10°C, compte tenu de la présence de certains composants susceptibles de cristalliser et de former des dépôts à cette température.

The viscosity of the additive compositions F3 and F5 at 20, 40 and -10 ° C. is measured according to standard NF EN ISO 3104 as well as their storage stability over time according to the method detailed below:

• each pure additive composition is placed in a frustoconical transparent glass flask which is left closed at a selected constant temperature; the composition tested is considered to be stable and homogeneous at the chosen temperature if it does not have, for more than 10 days, at said temperature, that is to say, a demixed liquid phase whose proportion is greater than 0.5% of its volume, either sediment or solid deposit greater than 0.05% of its volume. Stability tests were carried out at two different temperatures:
• - at laboratory temperature (approximately 20 ° C) which corresponds to the standard conditions of the test
• - at -10 ° C, given the presence of certain components that can crystallize and form deposits at this temperature.

The results are summarized in Table 4 below. <b> Table 4 </ b> Characterization unit additives F5 F3 Viscosity 20 ° C mm ² / s 7,486 8.451 Viscosity 40 ° C mm ² / s 4,744 5,322 Viscosity -10 ° C mm ² / s 30.28 33.96 Frustoconical flask stability Ambient temperature (20 ° C) for 10 days - 0.05% whitish demixing t = 10 days black deposit <0.05% v Frustoconical flask stability -10 ° C for 10 days - no stripping or deposit no stripping or deposit MV @ 15 ° C kg / m ³ 899.9 896.2

Example 2 - Evaluation of the effect of compositions F1 to F5 on diesel iniector fouling (direct injection) according to the XUD9 procedure.

Injector fouling tests according to the XUD9 procedure were carried out on 5 non-road diesel compositions B7 additive with the compositions F1 to F5 of Example 1 respectively as well as on the same virgin non-road B7 diesel evaluated at the beginning and at the end of the series so as to frame the results and check the stability of the engine.

The fouling test implemented has the following characteristics: The objective of this test is to evaluate the performance of the fuels and / or additive compositions with respect to the fouling of the injectors on a Peugeot engine XUD9 A / L four-cylinder and indirect injection Diesel.

We begin the test with a Peugeot XUD9 A / L engine with four cylinders and indirect injection diesel equipped with clean injectors whose flow was previously determined. The engine follows a determined test cycle for 10 hours and 3 minutes (repetition of the same cycle 134 times). At the end of the test, the injector flow is again evaluated. The quantity of fuel required for the test is 45 L. The loss of flow is measured on the four injectors. The results are expressed as percentage loss of flow for different needle lifts. The fouling values are usually compared to 0.1 mm needle lift because they are more discriminating and more precise and repeatable (repeatability <5%). <b> Table 5 </ b> Engine test results in XUD9 procedure: GOM B7 additive with 1000ppm vol./vol. Fi composition Fouling tests compositions Level of injector fouling * (%) (* average of 4 injectors) Gain / average of trials 0 and 6 (%) Trial 0 GOM B7 EN590 72 0.8 Trial 1 GOM B7 + F1 65.8 5.4 Trial 2 GOM B7 + F2 70.5 0.7 Trial 3 GOM B7 + F3 60.7 10.5 Trial 4 GOM B7 + F4 60.9 10.3 Trial 5 GOM B7 + F5 61.2 10 Trial 6 GOM B7 EN590 70.4 0.8 Average Tests 0 + 6 GOM B7 EN590 71.2

Non-road diesel fuel containing 7% (vol / vol) or (v / v) EMAG and meeting the tested blank EN590 standard has a fouling level of around 70% (72% at baseline and 70% at baseline). 4% at the end of the series). All the additive compositions tested have a level of fouling ranging from 60.7 to 10.5%, which is equivalent to or lower than that of the virgin B7 non-road diesel test. The best cases measured have a gain greater than or equal to 10%.

It can be seen that the compositions F1, F3, F4 and F5 have a more favorable effect for limiting the fouling of the XUD9 injectors.

Example 3 - Evaluation of Oxidation Stability

The oxidation stability of non-road diesel compounds B7 (GOM B7) additive with one of the additive compositions F1 to F5 according to the Rancimat method (standard EN15751) and for comparison that of non-additive non-road diesel is measured. . The results are shown in Table 6. <b> Table 6 </ b> Oxidation stability according to EN 15751: GOM B7 additive with 1000ppm vol./vol. Fi composition Stability tests formulations Induction time (h) Gain / GOM B7 blank (h) Trial 0 GOM B7 EN590 18 Trial 1 GOM B7 + F1 33 15 Trial 2 GOM B7 + F2 > 48 > 30 Trial 3 GOM B7 + F3 40 22 Trial 4 GOM B7 + F4 28 10 Trial 5 GOM B7 + F5 28 10

It is found that the additivation of non-road diesel improves the induction time (gain of 10 to> 38 hours compared to non-additive fuel)

The oxidation stability of non-road diesel compositions B7 which have been additive-treated with one of the additive compositions Fi according to the method detailed in standard ISO 12205 (gum content) and according to the method detailed in the ISO 6618 standard ( variation of the acid number).

The results relating to the formation of gums are shown in Table 7 and those relating to the acid number are shown in Table 8. <b> Table 7 </ b> Oxidation stability according to EN 12205 at 115 ° C: GOM B7 additive with 1000ppm vol./vol. Fi composition Stability tests compositions Rubber content (g / m ³ ) Gain / GOM B7 virgin (g / m ³ ) Trial 0 GOM B7 EN590 29 Trial 1 GOM B7 + F1 24 5 Trial 2 GOM B7 + F2 21 8 Trial 3 GOM B7 + F3 11 18 Trial 5 GOM B7 + F5 14 15 Variation of acid number ISO 6618 (mg KOH / g): GOM B7 additive with 1000ppm vol./vol. Fi composition Stability tests compositions Delta TAN (mg KOH / g) Trial 0 GOM B7 EN590 4.73 Trial 1 GOM B7 + F1 0.02 Trial 2 GOM B7 + F2 0.95 Trial 3 GOM B7 + F3 0.4 Trial 4 GOM B7 + F4 0.81 Trial 5 GOM B7 + F5 0.71

It is found that the non-road diesel additives with the compositions F1 to F5 have a variation in gum content and a variation in acid number limited compared to the non-additive gas oil. Formulations F3 and F5 are the most effective for limiting the formation of gums (Table 7). As regards the variation of the acid number, it is found that the F1 and F3 compositions are the most effective for limiting the evolution of the acidity (Table 8).

Example 4 - Evaluation of resistance to contact with metals

• une plaque métallique de zinc ou de cuivre est mise en contact avec 100 mL du carburant dans un flacon de verre de 125 mL; la lame métallique est complètement immergée pendant 7 jours à température ambiante (environ 20 °C). La surface métallique en contact avec le carburant est de 10 cm². Après cette période de contact, on dose les métaux cuivre ou zinc qui sont présents dans le carburant.

The effectiveness of the metal-contact resistance of the non-road-based additive gasoline compositions with or without an additive composition Fi is measured according to the method detailed below:

• a zinc or copper metal plate is contacted with 100 mL of the fuel in a 125 mL glass vial; the metal blade is completely immersed for 7 days at room temperature (about 20 ° C). The metal surface in contact with the fuel is 10 cm ² . After this period of contact, the copper or zinc metals that are present in the fuel are metered.

The results are shown in Table 9 below. <b> Table 9 </ b> Soaking test 7 days at 20 ° C: GOM B7 additive with 1000ppm vol./vol. Fi composition Metal extraction tests compositions Cu content (mg / kg) Zn content (mg / kg) Trial 0 GOM B7 EN590 3 6.7 Trial 1 GOM B7 + F1 2.95 3.1 Trial 2 GOM B7 + F2 <0,1 <0,1 Trial 3 GOM B7 + F3 <0,1 <0.2 Trial 4 GOM B7 + F4 5.7 10.2 Trial 5 GOM B7 + F5 <0,1 0.1

GOM B7 tested: GOM EN 590 having undergone soaking of a Cu blade and a Zn slide for 7 days at 20 ° C.

It is found that the compositions F2; F3 and F5 are the most effective in limiting the solution transition of copper and zinc.

Example 5

Oxidation stability tests according to the Rancimat method (standard EN 15751) are carried out on the fuel compositions previously brought into contact with metals such as zinc or copper as described in example 4. The results obtained according to the Rancimat method show a degradation of the stability of the GOM B7 compared to the stability tests on fuels that have not been put in contact with the metals of Example 3.

The results are shown in Table 10 below. <b> Table 10 </ b> GOM B7 at 6.7 ppm Zn additive with 1000ppm vol./vol. of composition F2 and F3 Stability tests formulations Induction time (h) Gain / GOM B7 blank (h) Trial 0 GOM B7 EN590 8 Trial 2 GOM B7 + F2 12 4 Trial 3 GOM B7 + F3 41 33

It can be seen that the fuel additive with F3 is the most efficient (the highest induction time).

Example 6

The filterability temperature is measured according to the NF EN 116 standard of several B0 (non-EMAG) or B7 type non-road diesel (with 7% vol / vol EMAG) EN 590 with or without additives at 1000 ppm v / v with the composition F3. The gain of TLF is also measured with respect to the same non-additive diesel. The results are shown in Table 11. <b> Table 11 </ b> Evaluation of cold holding TLF NF EN 116 - GOM B7 additive with 1000ppm vol./vol. of composition F3 GOM Initial TLF (° C) TLF GOM additive (° C) TLF gain / virgin GOM (° C) GOM B0 A -1 -14 13 GOM B7 B -2 -13 11 GOM B7 C -18 -22 4 GOM B7 D -15 -21 6 GOM B0 E -16 -28 12 GOM B7 F -14 -29 15

It can be seen that according to the gas oils tested, the composition F3 makes it possible to improve the TLF with a gain of 4 to 15 ° C. at the additivation level of 1000 ppm vol./vol.

Example 7 - Evaluation of the effect of the composition F3 on diesel injector fouling (direct injection) according to the procedure CEC DW10 SG-F-098

Tests of fouling of injectors according to the procedure CEC DW10 referenced SG-F-098 were carried out on a composition of diesel fuel B7 answering at least the specification EN 590, additive with the composition F3 of example 1, denoted G ₁ , as well as on the same composition of diesel B7 blank, rated G ₀ , evaluated at the beginning and end of the series so as to frame the results and check the stability of the engine. The test uses a DW10BTED4 engine developed by PSA Peugeot Citroën, with a displacement of 1998 cm ³ , with direct diesel injection, compliant with Euro 4 emissions standards if the vehicle is equipped with a particulate filter. Table 11 summarizes the main characteristics of the motor: Table 11 Architecture 4-cylinder in-line, overhead camshaft, equipped with a turbocharger and exhaust gas recirculation EGR 100kW @ 4000tr / min performances 320NM @ 2000tr / min Injection system Common rail with piezo injectors, 6 holes developed by Continental Automotive, Maximum injection pressure: 1660bar

• La procédure d'encrassement dure 32h. Les 32h sont réparties en quatre périodes de 8h entrecoupées de périodes de macération de 4h chacune pendant lesquelles le moteur est à l'arrêt. Pour accélérer l'encrassement des injecteurs, 1 ppm de zinc masse sous forme de neodécanoate de zinc de formule Zn(C₁₀H₁₉O₂)₂ est ajouté dans le carburant.

The fouling test implemented has the following characteristics:

• The fouling procedure lasts 32 hours. The 32h are divided into four periods of 8h interspersed with maceration periods of 4h each during which the engine is stopped. To accelerate the fouling of the injectors, 1 ppm of zinc mass in the form of zinc neodecanoate of formula Zn (C ₁₀ H ₁₉ O ₂ ) ₂ is added to the fuel.

The test evaluates the power loss of the motor after 32 hours of walking. Low power loss indicates low fouling. The additive composition will therefore be judged by its non-fouling nature and its ability to prevent deposits when it is introduced into the fuel in the presence of zinc.

At each cycle, the value of the power is measured on the twelfth step (4000tr / min full load). The result of the test is the loss of power measured on this point between the end of the test (linear average of the last 5 measurements) and the beginning of the test (linear average of the first 5 measurements).

The figure 1 shows the fouling obtained for the reference fuel G ₀ + 1 ppm Zn and for the fuel according to the invention G ₁ + 1ppm Zn.

From these measurements, a power loss value was determined for G ₀ + 1 ppm Zn of the order of -5.6% while no loss of power was observed for G1 + 1 ppm Zn.

These results show that the gas oil composition G ₁ according to the invention therefore has a non-fouling character. In addition, the additive composition F3 is remarkable in that it has a strong ability to prevent deposits when it is introduced into a diesel fuel in the presence of zinc.

Claims (15)

1. Additive compositions comprising the following components:

   a) at least one metal deactivator or chelating agent chosen from the amines substituted by N,N'-disalicylidene groups,

   b) at least one antioxidant of the hindered phenol type (alkylphenol),

   c) at least one dispersant and/or detergent,

   i) at least one metal passivator chosen from compounds comprising a triazole group, alone or in a mixture,
   and optionally

   d) at least one acid scavenger of the aliphatic, cycloaliphatic or aromatic amine type;

   e) at least one low-temperature performance additive,

   f) at least one tracer or marker,

   g) at least one fragrancing agent and/or agent for masking odours and/or reodorant,

   h) at least one biocide.
2. Additive compositions according to claim 1, comprising at least one hydrocarbon organic solvent and/or at least one compatibilizing agent or co-solvent.
3. Additive compositions according to claim 2, in which the metal passivator is chosen from the amines substituted by triazole groups, alone or in a mixture.
4. Additive compositions according to claim 3, in which the metal passivator is chosen from N,N-Bis(2-ethylhexyl)-1,2,4-triazol-1-ylmethanamine, (CAS 91273-04-0) and N,N'-bis-(2 ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine (CAS 80584-90-3), alone or in a mixture.
5. Additive compositions according to any one of claims 1 to 4, in which

   * the metal deactivators or chelating agents a) are chosen from the amines substituted by N,N'-disalicylidene groups, such as N,N'-disalicylidene 1,2-diaminopropane (DMD);

   * the antioxidants of alkylphenol type b) are chosen from the molecules comprising at least one hindered phenol group (alkylphenols), alone or in a mixture,

   * the dispersants and/or detergents c) are chosen from the substituted amines, the polyetheramines, the products of reaction between a phenol substituted by a hydrocarbon chain, an aldehyde, and an amine or polyamine or ammonia, carboxylic dispersants, aminated dispersants originating from the reaction between halogenated aliphatics of high molecular weight with amines or polyamines, polymeric dispersants obtained by polymerization of alkylacrylates or alkylmethacrylates (C8 to C30 alkyl chains), aminoalkylacrylates or acrylamides and acrylates substituted by poly-(oxyethylene) groups;

   * the optional acid scavengers d) are chosen from the aliphatic, cycloaliphatic and aromatic amines, preferably dimethylcyclohexyldiamine;

   * the optional low-temperature performance additives e) are chosen from the additives improving the pour point, the additives improving the cold filter plugging point (CFPP), additives improving the cloud point and/or the anti-sedimentation and/or paraffin dispersant additives,

   * the metal passivators are chosen from the amines substituted by triazole groups such as N,N-Bis(2-ethylhexyl)-1,2,4-triazol-1-ylmethanamine (CAS 91273-04-0) and the N,N'-bis-(2 ethylhexyl) -4-methyl-1H-benzotriazole amine (CAS 80584-90-3).
6. Additive compositions according to any one of claims 1 to 5, comprising at least

   a) at least one metal deactivator a) chosen from the amines substituted by N,N'-disalicylidene groups, such as N,N'-disalicylidene 1,2-diaminopropane (DMD),

   b) at least one antioxidant of the hindered phenol type b), chosen from the molecules comprising at least one hindered phenol group, alone or in a mixture,

   c) at least one dispersant and/or detergent c) chosen, preferably, from the PIBSIs,

   d) at least one acid scavenger of the amine type d),

   i) at least one metal passivator i) chosen from the amines substituted by triazole groups, such as benzotriazole, toluyltriazole
   and optionally

   e) at least one additive for improving low-temperature performance chosen from the EVA copolymers and/or VEOVA terpolymers e),

   f) at least one marker or tracer f),

   g) at least one fragrancing agent and/or agent for masking odours and/or reodorant, chosen from:

   * the organic tricyclic compounds described in EP 1,591,514 which are organic tricyclic compounds of formula (I) below

   

   in which the cyclopentane ring is saturated or unsaturated, and R1, R2, R3, identical or different, are chosen from hydrogen and the hydrocarbon radicals comprising from 1 to 10 carbon atoms and optionally comprising one or more heteroatoms
   as well as

   * the aliphatic or aromatic aldehydes such as vanillin,

   * the aliphatic or aromatic esters, such as benzyl acetate,

   * the alcohols, such as linalool, the phenylethyl alcohols,

   * the ketones, such as crystallized camphor, ethyl maltol,

   * the essential oils, such as essential oil derived from citrus fruits and/or

   * mixtures thereof,

   and preferably the mixture of at least one organic tricyclic compound and at least one aldehyde, ester, hydroxide, ketone, essential oil,

   h) at least one biocide additive h).
7. Additive compositions according to any one of claims 1 to 6, comprising:

   - from 0.1 to 5% by mass and preferably from 1 to 2% by mass of metal deactivator a),

   - from 1 to 30% by mass and preferably from 2.5 to 10% by mass of antioxidant(s) of the hindered phenol type (alkylphenol) b),

   - from 0.5 to 20% by mass and preferably from 1 to 10% by mass of dispersant(s) and/or detergent(s) c),

   - from 0 to 20% by mass, preferably from 0.5 to 20% by mass and advantageously from 1 to 10% by mass of acid scavengers d),

   - from 0 to 30% by mass and preferably from 10 to 20% by mass of low-temperature performance additive(s) e),

   - from 0 to 5% by mass and preferably from 0.2 to 5% by mass of tracer(s) f),

   - from 0 to 10% by mass and preferably from 2 to 5% by mass of fragrancing agent(s) and/or agent(s) for masking odours and/or reodorant(s) g),

   - from 0 to 20% by mass and preferably from 5 to 10% by mass and advantageously from 1 to 2% by mass of biocide(s) h),

   - up to 5% by mass, preferably from 0.1 to 5% by mass, more preferentially from 0.5 to 3.5% by mass of metal passivator(s) i)

   - from 10 to 80% by mass and preferably from 20 to 50% by mass of hydrocarbon organic solvent(s),

   - from 10 to 60% by mass and preferably from 20 to 40% by mass of compatibilizing agent(s) or co-solvent(s).
8. Method for the preparation of the compositions as defined in any one of claims 1 to 7 by mixing, preferably at ambient temperature, components a) to c) and component i), and optionally components e) to h) and/or solvent(s) and/or compatibilizing agents and/or other components, in one or more steps.
9. Liquid fuel composition of the gas oil type comprising:

   - a majority part of a mixture based on liquid hydrocarbons having distillation temperatures comprised between 150 and 380°C;

   - a minority part comprising at least one additive composition as defined in one of claims 1 to 7, and optionally one or more additives other than those of the additive composition(s) according to the invention.
10. Liquid fuel composition of the diesel type according to claim 9 comprising from 100 to 2000 ppm, preferably from 250 to 1000 ppm by mass of additive composition(s) as defined in one of claims 1 to 7.
11. Liquid fuel composition of the diesel type according to one of claims 9 and 10, characterized in that the other additives are chosen from the lubricity or anti-wear additives, combustion-improving agents, anti-foaming agents, anticorrosion agents, detergents.
12. Liquid fuel composition of the diesel type according to any one of claims 9 to 11, characterized in that the other additives are incorporated in quantities ranging from 50 to 1500 ppm by mass.
13. Liquid fuel composition of the non-road diesel type according to any one of claims 9 to 12, comprising at least seven parts by volume of at least one product of renewable origin.
14. Liquid fuel composition of the non-road diesel type according to claim 13, in which the product of renewable origin is chosen from the fatty acid esters, essentially or exclusively of animal or vegetable origin.
15. Use of the additive compositions according to one of claims 1 to 7, for improving the storage stability, the oxidation resistance, the low-temperature performance, and more particularly the engine performances of the diesel fuel.

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