ADDITIVE COMPOSITIONS THAT IMPROVE THE STABILITY AND THE ENGINE
PERFORMANCES OF DIESEL FUELS
Technical field
The present invention relates to additive compositions making it possible to improve
the stability and engine performances of the gas oils used as diesel fuel, in particular
gas oils of the non-road type.
Since the entry into force of the decree of 10 December 2010, in France the term
"gazole non routier" [non-road gas oil] denotes a mixture of hydrocarbons of mineral
origin or from synthesis with 7 parts by volume of fatty acid methyl esters according
to the minimum requirements of the standard EN 590 or any other standard or
specification in force in the EU having a maximum sulphur content of 20 mglkg at the
distribution stage.
Previously, domestic fuel oil (dfo) was intended both for heating applications and
engine applications; since this Decree, the products are differentiated, i.e. distributed
in different distribution networks and required to be stored in separate storage
facilities in different networks according to their intended use: stationary applications
(heating) on the one hand, and non-stationary applications (non-road gas oil). For
heating applications, the fuel oil has a sulphur content of 1,000 pm mass whereas
the non-road gas oil has a sulphur content less than or equal to 10 ppm by mass
(tolerance 20 ppm); the cetane number of domestic fuel oil is 40 whereas that of
non-road gas oil is 51 (better flammability)
In France the use of non-road gas oil, marketed via a specific distribution network
and subject to a diferent tax regime to that of motor vehicles is mandatory for
* non-road mobile machinery, such as
construction and civil engineering equipment, in particular bulldozers, all-terrain
trucks, excavators, tractors and loaders,
road maintenance equipment
snow ploughs and street sweepers,
self-propelled agricultural vehicles, forestry equipment,
handling equipment, mobile cranes, power lift trucks,
self-propelled ladders and platforms,
5 ground airport assistance equipment
industrial drilling equipment,
compressors and motor-driven pumps,
railway locomotives,
truck-mounted generators or hydraulic power units,
10 * agricultural or forestry tractors,
* pleasure boats,
* inland navigation boats.
For environmental reasons andlor because of the availability of resources,
15 regulations in many countries encourage the introduction of constantly increasing
quantities of products of renewable origin, such as fatty acid esters, into
conventional gas oil and non-road gas oil. Thus, at present in the EU, the on-road
gas oil used as diesel fuel can contain 7 parts by volume of fatty acid esters,
generally fatty acid methyl esters (FAME), essentially or exclusively of vegetable or
20 animal origin (vegetable andlor animal oil esters, in particular vegetable oil methyl
esters or VOMEs).
State of the art
In the past, the machinery engines operating with non-road gas oil were deemed to
25 be unsophisticated and undemanding but the specifications of these engines have
developed and are increasingly operating according to technologies as advanced
(very high pressure direct injection technologies) as those of on-road motor vehicles.
Standard-grade non-road gas oil (currently in compliance with the standard EN
3 0 590) sometimes poses problems in terms of:
- stability during storage and use: in the case of prolonged storage or in the case
of use under conditions of high pressures or temperatures: the antioxidants
incorporated in the FAME are not always sufficient to stabilize the product and
do not make it possible to combat the action of metals (catalysts of oxidation and
5 degradation phenomena). This instability of the fuel can lead to phenomena of
fouling of the filters and injection systems.
- extraction of metals: the FAMEs and their by-products have a tendency to
promote the extraction of metals with which they are brought into contact, for
example transport, storage materials and1 or parts or components.
10 - low-temperature performance: in particular for non-road gas oils, given the
prolonged period of storage of such fuels which is sometimes greater than 6
months, and taking account of the seasonal nature of the specifications in the
winter period or between seasons, the low-temperature performance can be
problematic for the user (problems of crystallization, sedimentation, filter
15 plugging etc.).
There is therefore a need to improve the quality of the gas oils and, in particular,
to provide novel additive compositions capable of improving the properties of the
gas oils irrespective of their intended use or their composition (with or without
20 products of renewable origin): on-road gas oil or non-road gas oil, of types BO to
B7.
Disclosure of the invention
The present invention proposes a high-grade on-road or non-road gas oil which has
2 5 improved properties compared with the corresponding standard-grade on-road or
non-road gas oil (EN 590). Within the meaning of the present invention, several of
the properties of the standard gas oil are improved, and in particular the oxidation
resistance, storage stability, thermal stability and engine performances (reduction in
fouling of the injectors; the following improvements are also possible: reduction in
30 the loss of power; reduction in the tendency of the filters to clog etc.); lowtemperature
performance (CFPP and pour point).
The invention also relates to additive compositions capable of improving the
properties of the gas oil, in particular of the non-road gas oil, such as oxidation
resistance, storage stability, thermal stability, engine performances (reduction in
5 fouling of the injectors); low-temperature performance (CFPP and pour point),
reduction in loss of power, reduction the tendency of the filters to clog etc.) can also
be improved.
This additive composition added to the fuel (on-road or non-road gas oil) more
10 particularly makes it possible to reduce the tendency of the injectors to be fouled by
the fuel. The fouling of the injectors can lead to losses of power but also a
degradation of combustion which is responsible for an increase in pollutant
emissions.
15 Summary description of the drawings
Other advantages and characteristics will become more clearly apparent from the
following description of particular embodiments of the invention given as nonlimitative
examples and represented in the single attached drawing in which Figure 1
represents the loss of power (in %) as a function of the duration (in hours) of an
20 injector fouling test according to the CEC DW10 procedure referenced SG-F-098, on
a diesel fuel composition, reference gas oil GO and a diesel gas oil fuel composition
GI according to the present invention.
A first subject of the invention relates to additive compositions comprising the
25 following components:
a) at least one metal deactivator or chelating agent,
b) at least one antioxidant of the hindered phenol type (alkylphenol),
c) at least one dispersant,
and optionally
30 d) at least one acidity neutralizer (acid scavenger) of aliphatic, cycloaliphatic or
aromatic amine type,
e) at least one low-temperature performance additive,
9 at least one tracer or marker,
g) at least one fragrancing agent andlor agent for masking odours andlor
reodorant,
h) at least one biocide,
i) at least one metal passivator.
According to a particularly preferred embodiment, the additive compositions
comprise the following components:
a) at least one metal deactivator or chelating agent,
b) at least one antioxidant of the hindered phenol type (alkylphenol),
c) at least one dispersant,
i) at least one metal passivator,
and optionally
15 d) at least one acidity neutralizer (acid scavenger) of the aliphatic, cycloaliphatic
or aromatic amine type,
e) at least one low-temperature performance additive,
9 at least one tracer or marker,
g) at least one fragrancing agent andlor agent for masking odours andlor
reodorant,
h) at least one biocide.
According to a particular embodiment, the metal passivator i) is chosen from the
triazole derivatives, alone or in a mixture, for example benzotriazole derivatives. By
25 "triazole derivatives" is meant all of the compounds comprising a triazole unit, i.e. a
5-membered aromatic cyclic unit, comprising two double bonds and 3 nitrogen
atoms. According to the position of the nitrogen atoms, a distinction is drawn
between the 1,2,3-triazole units (called V-triazoles) and the 1,2,4-triazole units
(called S-triazoles). As examples of triazole units, benzotriazole or tolyltriazole can
30 be mentioned.
The metal passivator i) can be chosen from the amines substituted by triazole
groups, alone or in a mixture. By "triazole group" is meant any substituent containing
a triazole unit as defined above.
5 The metal passivator(s) i) can, for example, be chosen from N,N-Bis(2-ethylhexy1)-
1,2,4-triazol-I-ylmethanamine (CAS 91273-04-0) and N,N1-bis-(2-ethylhexyl)-4-
methyl-IH-benzotriazole amine (CAS 80584-90-3), alone or in a mixture and the
passivators described on page 5 of US200610272597 cited by way of example and
the content of which is incorporated by way of reference.
10 In particular, the metal passivator is advantageously chosen from N,N-bis(2-
ethylhexy1)-I ,2,4-triazol-I -ylmethanamine (CAS 91 273-04-0) and N,N'-bis-(2-
ethylhexy1)-4-methyl-1H-benzotriazole amine (CAS 80584-90-3), alone or in a
mixture.
15 According to the nature and the miscibility of constituents a) to i) of the additive
composition according to the invention, with gas oil, the additive composition can
also contain one or more hydrocarbon organic solvents and optionally at least one
compatibilizing agent or co-solvent.
20 Preferably, the additive composition also comprises at least one hydrocarbon
organic solvent andlor at least one compatibilizing agent or co-solvent.
The metal deactivator(s) or chelating agents a) can be chosen from amines
substituted by N,N'-disalicylidene groups, such as N,N'-disalicylidene 1,2-
25 diaminopropane (DMD).
The antioxidant or antioxidants b) can be chosen from molecules comprising at least
one hindered phenol group (alkylphenols), alone or in a mixture; as examples of
antioxidants of the hindered phenol type, there can be mentioned di-t-butyl-2,6
30 methyl-4 phenol (BHT), t-butyl hydroquinone (TBHQ), 2,6 and 2,4 di-t-butyl phenol,
2,4-dimethyl-6-t-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene bis (2,6-di-tbutyl
phenol) (CAS No. 11 8-82-I), alone or in a mixture.
The dispersant(s) c) can for example be chosen from:
5 o substituted amines such as N-polyisobutene amine R1-NH2, Npolyisobutenethylenediamine
R1-NH-R2-NH2, or also the polysiobutenesuccinimides
of formula
where R1 represents a polyisobutene group with a molecular mass comprised
10 between 140 and 5000 and preferably between 500 and 2000 or, preferably,
between 750 and 1250;
R2 represents at least one of the following segments -CH2-CH2-, CH2-CH2-
CH2, -CH-CH(CH3)-
and x an integer comprised between 1 and 6.
15
The polyethylene amines 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, lnterscience Publishers, New York (1950).
20 o - the polyetheramines of formula:
where:
R is an alkyl group comprising from 1 to 30 carbon atoms;
R1 and R2 are each independently a hydrogen atom, an alkyl chain of from 1 to 6
carbon atoms or -0-CHRI -CHR2-;
A is an amine or N-alkylamine with 1 to 20 carbon atoms in the alkyl chain, an N,Ndialkylamine
having from 1 to 20 carbon atoms in each alkyl group, or a polyamine
5 with 2 to 12 nitrogen atoms and 2 to 40 carbon atoms.
and x ranging from 5 to 100;
Such polyetheramines are for example marketed by BASF, HUNTSMAN or
CHEVRON.
10 o the products of reaction between a phenol substituted by a hydrocarbon chain,
an aldehyde and an amine or polyamine or ammonia. The alkyl group of the
alkylated phenol can be constituted by 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; l-butene, isobutylene and 1 decene). The polyolefins
15 particularly used are polyisobutene and/or polypropylene. The polyolefins generally
have a weight average molecular weight Mw comprised between 140 and 5000 and
preferably between 500 and 2000 or preferably between 750 and 1250.
The alkylphenols can be prepared by alkylation reaction between a phenol and an
20 olefin or a polyolefin such as polyisobutylene or polypropylene.
The aldehyde used can contain from 1 to 10 carbon atoms, generally formaldehyde
or paraformaldehyde.
The amine used can be an amine or a polyamine including the alkanolamines having
one or more hydroxy groups. The amines used are generally chosen from
2 5 ethanolamine, the 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 the patent US 5 697 988.
30 o other dispersants, such as:
carboxylic dispersants such as those described in US 3,219,666;
aminated dispersants originating 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
5 alkylmethacrylates (C8 to C30 alkyl chains), aminoalkylacrylates or acrylarnides and
acrylates substituted by poly-(oxyethylene) groups. Examples of polymeric
dispersants are for example described in US 3,329,658 and US 3,702,300.
The optional acid neutralizer(s) or scavenger(s) d) can be chosen from the aliphatic,
10 cycloaliphatic and aromatic amines. Preferably, it is preferred to use
dimethylcyclohexyldiamine as acidity neutralizer.
The low-temperature performance additive or additives e) can be chosen from
additives improving the pour point, additives improving the cold filter plugging point
15 (CFPP), additives improving the cloud point andlor the anti-sedimentation additives
andlor paraffin dispersants.
As examples of additives improving the pour-point and filtrability (CFls), there can be
mentioned the ethylene and vinyl acetate (EVA) copolymers andlor ethylene and
vinyl propionate (EVP) copolymers.
20
As examples of additives improving the CFPP, there can be mentioned the multifunctional
cold operability additives chosen from particular from the group constituted
by the polymers based on olefin and alkenyl nitrate such as those described in
EP 573 490.
2 5
As examples of additives improving the cloud point, there can be mentioned nonlimitatively
the compounds chosen from the group constituted by the long-chain
olefin/(meth)acrylic esterlmaleimide terpolymers, and fumariclmaleic acid ester
polymers. Examples of such additives are given in EP 71 513, EP 100 248,
3 0 FR 2 528 051, FR 2 528 051, FR 2 528 423, EPI 12 195, EP 1 727 58, EP 271 385
and EP 291367.
As examples of anti-sedimentation additives and/or paraffin dispersants, it is
possible to use in particular anti-sedimentation (but non-limitatively) additives chosen
from the group constituted by the (meth)acrylic acid 1 polyamine-amidified alkyl
(meth)acrylate copolymers, polyamine alkenylsuccinimides, phthalamic acid and
5 double-chain fatty amine derivatives; alkylphenollaldehyde 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 200510223631; US 5 998 530; WO 93114178.
Preferably, the additive compositions according to the invention contain
10 ethylenelvinyl acetate (EVA) copolymers andlor ethylenelvinyl acetatelvinyl
versatate (VEOVA) terpolymers andlor ethylenelvinyl acetate1 acrylic ester (2-
ethylhexyl acrylate) terpolymers as low-temperature additive e)
The optional marker(s) or tracer(s) 9 can in particular be chosen from the following
15 aliphatic or cycloaliphatic esters:
3a145, ,6,7,7a-hexahydro-4,7-methano-I h-inden-5 (or 6)-yl isobutyrate (CAS
67634-20-2)
tricyclodecenyl propionate (CAS 1751 1-60-3)
cis 3 hexenyl acetate (CAS 3681-71-8)
20 ethyl linalool (CAS 10339-55-6)
prenyl acetate (CAS 1 1 91 -1 6-8)
ethyl myristate (CAS 124-06-1)
para-tert-butyl cyclohexyl acetate (CAS 3221 0-23-4)
butyl acetate (CAS 123-86-4),
25 4,7-methano-I h-inden-6-01, 3a14,5,6,7,7a-hexahydro-a, cetate (CAS 5413 -60-5)
ethyl caprate (CAS 1 10-38-3)
The optional fragrancing agent(s) or agent(s) for masking odours andlor reodorant(s)
g) can be chosen from:
3 0 * 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
5 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,
10 * the essential oils, such as essential oil derived from citrus fruits
alone or in a mixture.
Advantageously, it is preferable to use as fragrancing agent, agent for masking
odours or reodorant g), a mixture of at least one organic tricyclic compound and at
least one aldehyde, ester, hydroxide, ketone, essential oil as defined above.
15
The biocide(s) h) can be chosen from:
the 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-
20 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: 21 564-17-0);
quaternary ammonium salts in the form of chlorides obtained from C12-C18 alkyl
benzene or alkyl dimethyl benzene.
Certain components of the compositions according to the invention can have several
functionalitieS, typically marker and fragrancing agent: a component can be both
marker and fragrancing agent.
Preferably, the additive composition according to the invention comprises:
a) at least one metal sequestering agents 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, chosen from the
molecules comprising at least one hindered phenol group, alone or in a mixture;
as examples of antioxidants of the hindered phenol type, there can be mentioned
di-t-butyl-2,6 methyl-4 phenol (BHT), t-butyl hydroquinone (TBHQ), 2,6 or 2,4 di-tbutyl
phenol, 2,4-dimethyl-6-t-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene
bis (2,6-di-t-butyl phenol) (CAS No. 11 8-82-I), alone or in a mixture,
c) at least one dispersant and/or detergent, preferably chosen from the PIBSls,
d) at least one acidity neutralizer of the amine type, and optionally
e) at least one additive for improving low-temperature performance chosen from
the EVA copolymers and/or VEOVA terpolymers,
f) at least one marker or tracer,
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
* mixtures thereof,
and preferably, the mixture of at least one organic tricyclic compound and at least
one aldehyde, ester, hydroxide, ketone, essential oil, and/or
h) at least one biocide additive,
i) at least one metal passivator i) chosen from the amines substituted by triazole
groups, such as benzotriazole, toluyltriazole.
According to a particularly preferred embodiment, the additive composition according
to the invention comprises:
a) at least one metal-sequestering agent chosen from the amines substituted by
N,N'-disalicylidene groups, such as N,N9-disalicylidene 1,2-diaminopropane
(DMD),
b) at least one antioxidant of the hindered phenol type, chosen from the
molecules comprising at least one hindered phenol group, alone or in a mixture;
as examples of antioxidants of the hindered phenol type, there can be mentioned
di-t-butyl-2,6 methyl-4 phenol (BHT), t-butyl hydroquinone (TBHQ), 2,6 or 2,4 di-tbutyl
phenol, 2,4-dimethyl-6-t-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene
bis (2,6-di-t-butyl phenol) (CAS No. 118-82-I), alone or in a mixture, and from the
molecules generally,
c) at least one dispersant and/or detergent, chosen preferably from the PIBSls,
d) at least one acidity neutralizer of the amine type,
i) at least one metal passivator i) chosen from the amines substituted by triazole
groups, such as benzotriazole, toluyltriazole,
and optionally
5 e) at least one additive for improving low-temperature performance chosen from
the EVA copolymers andlor VEOVA terpolymers,
f) at least one marker or tracer,
h) at least one biocide additive, andlor
g) at least one fragrancing agent andlor agent for masking odours andlor
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
* mixtures thereof,
and preferably, the mixture of at least one organic tricyclic compound and at least
one aldehyde, ester, hydroxide, ketone, essential oil.
Apart from the components described previously, the additive composition according
5 to the invention can contain, apart from the additive(s) according to the invention,
one or more other additives, different from the constituents a) to i), and solvent(s)
andlor co-solvents such as for example markers other than those corresponding to
the definition of the markers e) and in particular the markers mandated by
regulations, for example the Red dye at present required by the regulations in non-
10 road gas oil and domestic fuel oil, demulsifiers; the anti-static or conductivity
improving additives; lubricity additives, anti-wear agents andlor friction modifiers,
additives for improving combustion and in particular cetane improving additives, antifoaming
additives etc.
15 Preferably, the additive compositions according to the invention comprise:
- from 0.1 to 5% by mass and preferably from 1 to 2% by mass of metal
sequestering agent(s) 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),
20 - from 0.5 to 20% by mass and preferably from 1 to 10% by mass of dispersant(s)
andlor 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 acidity neutralizers d),
- from 0 to 30% by mass and preferably from 10 to 20% by mass of low-
25 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)
andlor agent(s) for masking odours andlor reodorant(s) g),
- from 0 to 20% by mass and preferably from 5 to 10% by mass and advantageously
3 0 from 1 to 2% by mass of biocide(s) h),
-from 0 to 5% by mass or up to 5% by mass, preferably from 0.1 to 5%, more
preferentially from 0.5 to 3.5%, even more preferentially from 1 to 2% by mass of
metal passivator(s) i),
- from 10 to 80% by mass and preferably from 20 to 50% by mass of
5 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).
According to a second subject, the invention relates to a method for the preparation
10 of the additive compositions as defined above, by mixing, preferably at ambient
temperature, components a) to c), and optionally e) to i) of said compositions and/or
solvent(s) and/or compatibilizing agent@), in one or more steps by any suitable
mixing means.
15 According to a particular embodiment, the method for the preparation of 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) to h) of said
compositions and/or solvent(s) and/or compatibilizing agent@), in one or more steps
by any suitable mixing means.
20
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.
2 5 The additive compositions according to the invention have the additional advantage
of being stable in storage for at least several months at temperatures generally
ranging from -15°C to +40°C and can therefore be stored, for example in a depot, at
the refinery, before being mixed with standard gas oil or non-road gas oil.
30 According to a third subject the invention relates to a 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, preferably between 160 and
370°C, more preferentially between 180 and 370°C. These mixtures generally
originate from middle distillate-type cuts, originating from refineries and/or from
agrofuels andlor from biofuels and/or from biomass and/or from synthetic fuels, and
in particular from kerosene cuts generally rich in aromatic compounds (benzene, etc.)
- a minority part comprising at least one additive composition as defined above, and
optionally one or more additives other than those of the additive composition(s)
according to the invention, which may or may not be in the form of a package of
additives.
By "fuel" is meant a fuel which powers an internal combustion engine. In particular, a
liquid fuel of the gas oil type is considered to be a fuel which powers a diesel type
engine.
By "majority part" is meant the fact that the liquid fuel composition of the gas oil type
comprises at least 50% by mass of the mixture based on liquid hydrocarbons.
The mixture based on liquid hydrocarbons is, advantageously, constituted by any
mixture of hydrocarbons capable of being used as diesel fuel. Diesel fuels generally
comprise hydrocarbon cuts having a distillation range (determined according to the
standard ASTM D 86) comprised between 150 and 380°C, with an initial boiling point
comprised between 150 and 180°C and a final boiling point comprised between 340
and 380°C. The density at 15°C of the gas oils is in a standard fashion comprised
between 0.81 0 and 0.860.
According to a particular embodiment, the liquid fuel composition of the gas oil type
can comprise a product of renewable origin such as fatty acid esters. The renewable
product content in the liquid fuel composition of the gas oil type is, advantageously,
at least 0.2% by mass. The liquid fuel composition of the gas oil type can comprise
at least seven parts by volume of at least one product of renewable origin. The
product of renewable origin is chosen from the fatty acid esters, essentially or
exclusively of animal or vegetable origin. The fatty acid esters are advantageously
fatty acid methyl esters (FAMEs), essentially or exclusively of vegetable or animal
origin, for example vegetable and/or animal oil esters, in particular vegetable oil
5 methyl esters or VOMEs.
Preferably, the liquid fuel composition of the on-road or non-road gas oil type
according to the invention comprises from 100 to 2000 ppm, preferably from 250 to
1500 ppm, more preferentially from 250 to 1000 ppm by mass of additive
10 composition(s) as defined above.
The other optional additives are generally incorporated in quantities ranging from 50
to 1500 ppm by mass.
15 As examples of other optional additives, there can be mentioned, non-limitatively,
lubricity or anti-wear additives, combustion improvers, anti-foaming agents,
anticorrosion agents, detergents etc.
The liquid fuel compositions of the gas oil type according to the invention can be
20 prepared by mixing the liquid fuel, additive composition(s) according to the invention
and other optional additive(s), in one or more steps, generally at ambient
temperature. The scope of the invention would not be exceeded by separately
mixing the components of the additive composition according to the invention
(additives a) to c)), optionally additives d) to i), the solvent(s) and/or co-solvent(s)),
2 5 the other optional additives (in the form of a package or not) with the fuel of the gas
oil type.
According to a fourth subject, the invention relates to the use of the additive
compositions as described above as an agent for improving storage stability,
30 oxidation resistance, low-temperature performance and, more particularly, engine
performances in particular reduction in fouling (fouling and clogging) by gas oil fuels,
in particular, by non-road gas oil fuels.
The invention also relates to the use of the gas oil-based liquid fuel compositions
5 according to the invention as defined above as higher-grade fuels of the gas oil type,
i.e. having storage stability properties and, towards materials, oxidation resistance,
low-temperature performance and, more particularly, engine performances in
particular a reduction in fouling (fouling and clogging) greater than that of a standard
grade on-road and non-road gas oil (which, as a minimum, meets the specifications
10 of the standard EN 590).
The higher grade gas oil according to the invention, i.e. comprising at least one
additive composition according to the invention, can be advantageously used as fuel
for the engines of the non-road machinery listed in the Decree of 1011 211 0, namely
15 * non-road mobile machinery, such as
construction equipment, in particular bulldozers, all-terrain trucks, excavators,
tractors and loaders,
road maintenance equipment
snow ploughs and street sweepers,
20 self-propelled agricultural vehicles, forestry equipment,
handling equipment, mobile cranes, power lift trucks,
self-propelled ladders and platforms,
ground airport assistance equipment
industrial drilling equipment,
25 compressors and motor-driven pumps,
railway locomotives,
truck-mounted generators or hydraulic power units,
* agricultural or forestry tractors,
* pleasure boats,
30 * inland navigation boats.
Examples The characteristics of non-road gas oils in compliance with the decree of
10 December 2010, i.e. of standard grade non-road gas oils, are listed in Tables 1
and 2 below.
5
Table 1: Characteristics of non-road gas oil (decree of 10 December 201 0)
PROPERTIES UNIT LIMITS
Mini Maxi
Measured cetane index 51 .O
Calculated cetane index 45.0
Density (at 15°C) kg/m2 820 845
Polycyclic aromatic hydrocarbons % - 8.0
(mlm)
Flash point " C >55 -
Carbon residue (out of 10% distillation residue) %(m/m) - 0.30
Ash content Oh(m/m) - 0.01
Water content mglkg - 200
Total contamination mglkg - 24
Copper strip corrosion (3 h at 50°C) Rating Class 1
Oxidation stability 1 : g/m2 - 25
h 20 -
Oxidation stability 2: mg -
Acid number variation KOHIg
0.30
Lubricity: corrected wear scar diameter (wsd 1.4)
Clm -
at 60°C
460
Viscosity at 40% mm2/s 2.00 4.50
Distillation:
-Oh (v/v) condensed at 250°C: O h (vlv) - 65
-% (v/v) condensed at 350°C: % (vlv) 85 -
-point at which 95% (VN) condensed: " C - 360
Fatty acid ester content in compliance with the % (VN) - 7.0
decree of
** ** 201 0 relating to the characteristics of the fatty
acid methyl esters
Table 2: Characteristics of the non-road gas oil (decree of 1011 211 0) (continued)
SEASON DATE CLASS CFPP("C. max)
Summer 1 St April - 31 October B 0°C
Winter lSNovte mber - 31 E -1 5°C
March
Extreme cold non-road gas F -20°C
oil
CFPP: cold filter plugging point
Example 1- preparation of additive compositions F1 to F5
Several additive compositions are prepared by mixing at ambient temperature
several of the components listed below in proportions shown in Table 3
5 N,N1-disalicylidene 1,2-diaminopropane (metal-sequestering agent a)
BHT (alkylphenol type antioxidant) b)
PlBSl (dispersant c))
dicyclohexylamine (neutralizer d)
aromatic solvent (mixture of Solvarex 10 and 10 LN)
10 50150 by weight mixture of EVA copolymer and VEOVA terpolymer in solution in
aromatic solvent (CFPP additive e))
benzotriazole (metal passivator i))
Table 3
15
The viscosity of the additive compositions F3 and F5 at 20, 40 and -10°C is
measured according to the standard NF EN IS0 3104, as well as their storage
stability over time according to the method described in detail below:
each pure additive composition is placed in a transparent glass conical flask which is
2 0 left closed at a chosen constant temperature; the tested composition is considered to
be stable and homogeneous at the chosen temperature if, after 10 days at said
temperature, either it has not a demixed liquid phase the proportion of which would
be greater than 0.5% of its volume, or it has not sediment or solid deposit greater
F1
F2
F3
F4
F5
Components
a)
sequestering
agent
1
0
1.5
1
1
(% by mass)
b)
antioxidant
5
10
4.5
2.25
3
Solvent
80
7 5
76.25
79.75
79.5
d)
neutralizer
0
0
0.75
1.5
0.5
c)
dispersant
0
0
1.5
1.5
1
i)
passivator
0
1
1.5
0
1
e)
CFPP
14
14
14
14
14
than 0.05% of its volume. Stability tests were carried out at two different
temperatures:
- at laboratory temperature (approximately 20°C) which corresponds to standard
test conditions
- at -lO°C, taking account of the presence of certain components capable of
crystallizing and forming deposits at this temperature.
The results are shown in Table 4 below.
Table 4
Example 2 - Evaluation of the effect of the compositions F1 to F5 on the diesel
iniector fouling (direct iniection) according to the XUD9 procedure
Injector fouling tests according to the XUD9 procedure were carried out on 5
compositions of non-road gas oil B7 comprising respectively the compositions F1 to
F5 of Example 1, as well as on the same pure non-road gas oil B7 evaluated at the
start and at the end of the series so as provide a context for the results and verify 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 andlor of
additive compositions towards the fouling of the injectors on a four-cylinder Peugeot
XUD9 AIL engine with indirect diesel injection.
Characterization
Viscosity at 20°C
Viscosity at 40°C
Viscosity at -1 0°C
Conical flask stability
Ambient temperature (20°C)
for 10 days
conical flask stability
-1 0°C for 10 days
Density @5°CI
unit
m m2/s
mm2/s
mm2/s
-
-
kg/m3
Additives
F5
7.486
4.744
30.28
0.05% by vol.
whitish demixed
medium
no demixing
nor deposit
899.9
F3
8.451
5.322
33.96
t * 10 days
black deposit
~0.05%~
no demixing
nor deposit
896.2
The test was started with a four-cylinder Peugeot XUD9 AIL engine with indirect
diesel injection equipped with clean injectors the flow rate of which was determined
beforehand. The engine follows a defined test cycle for 10 hours and 3 minutes
(repetition of the same cycle 134 times). At the end of the test, the flow rate of the
5 injectors is again evaluated. The quantity of fuel required for the test is 45 L. The
loss of flow rate is measured on the four injectors. The results are expressed as a
percentage of loss of flow rate for different needle lifts. Usually the fouling values at
0.1 mm of needle lift are compared as they are more discriminatory and more
accurate and repeatable (repeatability < 5%).
10
Table 5
The non-road gas oil containing 7% (vollvol) or (vlv) of FAME and corresponding to
the standard EN590 for tested pure gas oil shows a level of fouling of the order of
15 70% (72% at the start and 70.4% at the end of the series). All the tested
compositions containing additives show a level of fouling ranging from 60.7 to 70.5%,
therefore equivalent to or less than that of the pure non-road gas oil B7 tested. The
best cases measured show a gain greater than or equal to 10%.
It is noted that the compositions F1, F3, F4 and F5 are more effective in limiting the
20 fouling of the XUD9 injectors.
Results of XUD9 engine tests procedure: GOM B7 with 1000 ppm vol./vol. of composition Fi
Fouling test
Test 0
Test 1
Test 2
Test 3
Test 4
Test 5
Test 6
Average of
Tests 0 +6
Compositions
GOM B7
EN590
GOM 87 + F1
GOM B7 + F2
GOM B7 + F3
GOM 87 + F4
GOM B7 + F5
GOM 87
EN590
GOM 87
EN590
Level of injector fouling * (%)
(* average of the 4 injectors)
72
65.8
70.5
60.7
60.9
61.2
70.4
71.2
Gain / average of tests
0 and 6 (%)
0.8
5.4
0.7
10.5
10.3
10
0.8
Example 3 - Evaluation of the oxidation stability
The oxidation stability of compositions of non-road gas oil B7 (GOM B7) comprising
one of the additive compositions F1 to F5 was measured according to the Rancimat
5 method (standard EN15751) and, by way of comparison, that of the non-road gas oil
without additives was also measured. The results are shown in Table 6.
Table 6
Oxidation stability according to EN 15751: GOM 87 with 1000 pprn vol./vol. of composition
Fi added
Stability Gain 1 pure GOM 87
tests Formulations Induction period (h) (h)
GOM B7
Test 0 EN590 18
Test 1 GOM 87 + F1 33 15
Test 2 GOM 87 + F2 > 48 >30
Test 3 GOM 87 + F3 40 22
Test 4 GOM 87 + F4 28 10
Test 5 GOM 87 + F5 28 10
10 It is noted that the presence of additives in non-road gas oil makes it possible to
improve the induction period (gain from 10 to >38 hours compared with the fuel
without additives).
The oxidation stability of compositions of non-road gas oil B7 comprising one of the
additive compositions Fi was measured according to the method described in detail
15 in the standard IS0 12205 (gum content) and according to the method described in
detail in the standard IS0 6618 (acid number variation).
The results relating to gum formation are shown in Table 7 and those relating to the
acid number are shown in Table 8.
20
Table 7
Oxidation stability according to EN 12205 at 115°C: GOM 87 with 1000 ppm vol./vol, of
composition Fi added
Stability
tests Compositions Gum content (g/m3) Gain 1 pure GOM 87 (g/m3)
GOM 87
Test 0 EN590 29
Test 1 GOM 87 + F1 24 5
Test 2 GOM 87 + F2 21 8
Test 3 GOM 87 + F3 11 18
Test 5 GOM 87 + F5 14 15
Table 8
Acid number variation IS0 6618 (mg KOHIg): GOM 87 with 1000 ppm vol./vol. of
composition Fi added
Stability tests Compositions Delta TAN (mg KOHIg)
Test 0 GOM 87 EN590 4.73
Test 1 GOM 87 + F1 0.02
Test 2 GOM B7 + F2 0.95
Test 3 GOM B7 + F3 0.4
Test 4 GOM B7 + F4 0.81
Test 5 GOM B7 + F5 0.71
5
It is noted that non-road gas oils comprising the compositions F1 to F5 have limited
gum content variation and acid number variation compared with gas oil without
additives. The formulations F3 and F5 are the most effective in limiting gum
formation (Table 7). As regards the acid number variation, it is noted that the
10 compositions F1 and F3 are the most effective for limiting the development of acidity
(Table 8).
Example 4 - Evaluation of the resistance to contact with metals
The effectiveness of the resistance to contact with metals of the non-road gas oil
15 compositions with or without an additive composition Fi added was measured
according to the method described in detail below:
a metal plate of zinc or copper is brought into contact with 100 mL of the fuel in a
125 mL glass flask; the metal strip is completely immersed for 7 days at ambient
temperature (approximately 20°C). The metal surface area in contact with the fuel is
10 cm2. After this period of contact, the copper or zinc metals which are present in
the fuel are assayed.
5 The results are shown in Table 9 below.
Table 9
Soaking test 7 days at 20°C: GOM B7 with 1000 ppm vol./vol. of composition Fi added
Metal extraction tests Compositions Cu content (mglkg) Zn content (mglkg)
Test 0 GOM B7 EN590 3 6.7
Test 1 GOM B7 + F1 2.95 3.1
Test 2 GOM B7 + F2 < 0.1 < 0.1
Test 3 GOM 87 + F3 < 0.1 < 0.2
Test 4 GOM 87 + F4 5.7 10.2
Test 5 GOM B7 + F5 < 0.1 0. I
GOM B7 tested: GOM EN 590 having been used for soaking a strip of Cu and a strip of Zn
10 for 7 days at 20°C.
It is noted that the compositions F2; F3 and F5 are the most effective in limiting the
dissolution of the copper and of the zinc.
Example 5
15 Oxidation stability tests according to the Rancimat method (standard EN15751) are
carried out on the fuel compositions brought into contact beforehand 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
with stability tests on fuels which have not been brought into contact with the metals
20 of Example 3.
The results are shown in Table 10 below.
Table 10
I I
GOM B7 with 6.7 ppm of Zn with 1000 ppm vol./vol. of composition F2 and F3 added
I I Induction period I Gain I pure GOM 87
Stability tests Formulations (h) (h)
Test 0 GOM 87 EN590 8
Test 2 GOM 87 + F2 12 4
Test 3 GOM B7 + F3 41 33
It is noted that the fuel with F3 added is the most effective (highest induction period).
Example 6
The cold filter plugging point according to the standard NF EN 116 of several EN 590
non-road gas oils of type BO (without FAME) or B7 (with 7% vol./vol. of FAME), with
or without 1000 ppm v/v of the composition F3 added, was measured. The CFPP
10 gain was also measured with respect to the same gas oil without additives. The
results are shown in Table 11.
Table 11
Evaluation of the low-temperature performance CFPP NF EN 116 - GOM 87 with 1000
ppm vol./vol. of composition F3 added
CFPP GOM with CFPP gain I pure
Initial CFPP additives GOM
GOM (" C) (" C) (" C)
GOM BO A -1 -14 13
GOM 87 B -2 -1 3 11
GOM 87 C -1 8 -22 4
GOM 87 D -1 5 -2 1 6
GOM BO E -1 6 -28 12
GOM B7 F -14 -29 15
It is noted that according to the gas oils tested, the composition F3 makes it possible
15 to improve the CFPP with a gain of 4 at 15°C with an additive content of 1000 ppm
vol./vol.
Example 7 - Evaluation of the effect of the composition F3 on diesel iniector fouling
/direct iniection) according to the CEC DW10 procedure SG-F-098
Injector fouling tests according to the CEC DWlO procedure referenced SG-F-098
were carried out on a gas oil composition 87 corresponding, as a minimum, to the
specification EN 590 comprising the composition F3 of Example 1, denoted GI, as
well as on the same composition of pure gas oil B7, denoted Go, evaluated at the
5 start and at the end of the series so as to provide a context for the results and verify
the stability of the engine.
The test uses a DWlOBTED4 engine developed by PSA Peugeot Citroen, having a
cylinder capacity of 1998 cm3, with direct diesel injection, in compliance with the
Euro 4 emission standards if the vehicle is equipped with a particulate trap. Table 11
10 summarizes the main characteristics of the engine:
Table 11
The fouling test implemented has the following characteristics:
The fouling procedure lasts 32 hours. The 32 hours are divided into four 8-hour
15 periods interspersed with periods of maceration, each lasting 4 hours, during which
the engine is stopped. In order to accelerate the fouling of the injectors, 1 ppm of
zinc by mass in the form of zinc neodecanoate of formula Zn(CloH1902)2 is added to
the fuel.
Configuration
Performances
Injection system
20 The test evaluates the loss of power of the engine after running for 32 hours. A slight
loss of power reflects slight fouling. The additive composition is therefore judged by
its non-fouling nature and its ability to prevent deposits when it is introduced into the
fuel in the presence of zinc.
4 in-line cylinders, overhead camshaft, equipped with a turbocharger
and exhaust gas recirculation (EGR)
100kW @ 4000 rpm
320NM @ 2000 rpm
Common rail with 6-hole piezo electric injectors, developed by
Continental Automotive, Maximum injection pressure: 1660 bar
25 At each cycle, the value of the power on the twelfth stroke (4000 rpm fully loaded) is
measured. The test result is the loss of power measured at this point between the
end of the test (linear average of the last 5 measurements) and the start of the test
(linear average of the first 5 measurements).
Figure 1 shows the fouling obtained for the reference fuel Go + 1 ppm Zn and for the
fuel according to the invention GI + 1 ppm Zn.
5 Based on these measurements, a power loss value for Go + 1 ppm Zn of the order
of -5.6% was determined whereas no loss of power was observed for GI + 1 ppm
Zn.
Consequently, these results show that the gas oil composition GI according to the
10 invention has a non-fouling nature. Moreover, the additive composition F3 is
remarkable in that it has a high capability for preventing deposits when it is
introduced into a gas oil fuel in the presence of zinc.

Claims
1. Additive compositions comprising the following components:
5 a) at least one metal deactivator or chelating agent,
b) at least one antioxidant of the hindered phenol type (alkylphenol),
c) at least one dispersant andlor detergent,
i) at least one metal passivator,
and optionally
d) at least one acid scavenger of the aliphatic, cycloaliphatic or aromatic amine
type;
e) at least one low-temperature performance additive,
9 at least one tracer or marker,
g) at least one fragrancing agent andlor agent for masking odours andlor
reodorant,
h) at least one biocide.
2. Additive compositions according to claim 1, comprising at least one hydrocarbon
organic solvent andlor at least one compatibilizing agent or co-solvent.
20
3. Additive compositions according to one of claims 1 and 2, in which the metal
passivator is chosen from the triazole derivatives, alone or in a mixture.
4. Additive compositions according to claim 3, in which the metal passivator is
2 5 chosen from the amines substituted by triazole groups, alone or in a mixture.
5. Additive compositions according to claim 4, in which the metal passivator is
chosen from N,N-Bis(2-ethylhexy1)-1,2,4-triazol-I- ylmethanamine, (CAS 912 73-04-0)
and N,N'-bis-(2 ethylhexy1)-4-methyl-1H-benzotriazole amine (CAS 80584-90-3),
30 alone or in a mixture.
6. Additive compositions according to any one of claims 1 to 5, 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);
5 * 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 andlor 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
10 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;
15 * 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 andlor the anti-sedimentation
20 and/or parafin 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-l-ylmethanamine (CAS 91273-04-0) and
the N,N'-bis-(2 ethylhexyl) -4-methyl-I H-benzotriazole amine (CAS 80584-90-3).
2 5 7. Additive compositions according to any one of claims 1 to 6, comprising at least
I
I a) at least one metal-sequestering agent 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
30 molecules comprising at least one hindered phenol group, alone or in a mixture,
c) at least one dispersant andlor detergent c) chosen, preferably, from the PIBSls,
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
5 e) at least one additive for improving low-temperature performance chosen from
the EVA copolymers andlor VEOVA terpolymers e),
f) at least one marker or tracer f),
g) at least one fragrancing agent andlor agent for masking odours andlor
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
* mixtures thereof, andlor
h) at least one biocide additive h),
and preferably the mixture of at least one organic tricyclic compound and at least
one aldehyde, ester, hydroxide, ketone, essential oil.
8. Additive compositions according to any one of claims 1 to 7, comprising:
5 - from 0.1 to 5% by mass and preferably from 1 to 2% by mass of metal
sequestering agent(s) 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)
10 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 lowtemperature
performance additive(s) e),
15 - 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),
20 - 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
25 compatibilizing agent(s) or co-solvent(s).
9. Method for the preparation of the compositions as defined in any one of claims 1
to 8 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
3 0 compatibilizing agents and/or other components, in one or more steps.
10. 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 8, and optionally one or more additives other than those of the additive
composition(s) according to the invention.
11. Liquid fuel composition of the gas oil type according to claim 10 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 8.
12. Liquid fuel composition of the gas oil type according to one of claims 10 and 11,
characterized in that the other additives are chosen from the lubricity or anti-wear
additives, combustion-improving agents, anti-foaming agents, anticorrosion agents,
detergents.
13. Liquid fuel composition of the gas oil type according to any one of claims 10 to
12, characterized in that the other additives are incorporated in quantities ranging
from 50 to 1500 ppm by mass.
14. Liquid fuel composition of the non-road gas oil type according to any one of
claims 10 to 13, comprising at least seven parts by volume of at least one product of
renewable origin.
15. Liquid fuel composition of the non-road gas oil type according to claim 14, in
which the product of renewable origin is chosen from the fatty acid esters, essentially
or exclusively of animal or vegetable origin.