EP2147966B1 - Additive for liquid fuel, liquid fuel containing same and its use for energy generation and/or heating and/or cooking devices - Google Patents

Description

Technical area

The present invention relates to a liquid fuel composition Burning Kerosene type or kerosene used for the production of energy, for heating or cooking for family or collective use.

These fuels are of the Burning Kerozene type, fuels having distillation temperatures between those of gasoline and those of diesel fuel.

• BUK C1 : Burning Kerozene de classe C1
• BUK C2 : Burning Kerozene de classe C2

On the Anglo-Saxon market, there are two types of Burning Kerozene

• BUK C1: Class C1 Burning Kerozene
• BUK C2: Burning Kerozene Class C2

BUK C1 is de-aromatized and desulfurized kerosene. The BUK C1 is intended for mobile heating appliances and has an excellent combustion quality.

The BUK C2 is standard kerosene for conventional heating systems and has a lower combustion quality than the BUK C1.

These liquid fuels are used for fixed energy production applications, for heating, especially in the building, and for cooking. These fuels are well suited for thermal appliances such as spray boilers, domestic boilers and slow burning stoves, especially AGA® stoves.

By way of example of fuels, mention may be made of some of the liquid fuels sold by the applicant under the name Kerdane® (equivalent to BUK C1) or Ketrul® (equivalent to BUK C2).

State of the art

In some combustion appliances such as spray stoves or slow-burning stoves, the liquid fuel passes through a thin feed pipe, usually metal, to reach the combustion chamber; the walls of this duct closest to the combustion chamber are subjected to very high temperatures for residence times which can be significant, more particularly for appliances where the fuel flow is low. This greatly increases risk of thermal degradation of the fuel and may lead to the formation of solid deposits on the walls of the duct, resulting in a reduction in the diameter available for the passage of the fuel and a possible reduction of the flow, or even an interruption of the supply of the combustion chamber. combustion.

To avoid this, the manufacturers of these devices advise their customers to clean the supply ducts every 6 months, to eliminate solid deposits detrimental to the smooth running of combustion. In some cases maintenance is required before 6 months of use.

US 2003/196372 discloses an additive package which avoids the degradation of hydrocarbon fuels and which comprises from 3.0 to 5.5% by weight of an aromatic amine antioxidant, from 1.2 to 2.7% by weight a hindered phenol type antioxidant, 0.05 to 1.5% by weight of a metal deactivator, 0.5 to 5% by weight of a corrosion inhibitor and a detergent.

Summary of the invention

The present invention proposes a new Burning Kerosene type liquid fuel composition or kerosene that can be used in energy production and / or heating and / or cooking appliances. This liquid fuel not only avoids the problems of clogging of the supply ducts from the fuel storage tank to the combustion chamber but also ensures excellent combustion quality while limiting the solid deposits at the burner, i.e. unburnt. It allows a specific additivation with the additive according to the invention for a class C2 BUK to achieve the combustion quality of a class C1 BUK on certain types of thermal appliances.

1. a) de 10 à 50% en masse d'au moins un agent anti-oxydant de type phénol ou phénol/amine, le ou les anti-oxydants de type phénol/amine étant préféré,
2. b) de 5 à 20% en masse d'au moins un passivateur de métal, notamment de cuivre, choisi parmi les amines substituées par des groupements triazoles ou par des groupements N,N'-disalicylidène,
3. c) de 1 à 10% en masse d'au moins un agent anti-corrosion choisi parmi les dérivés d'acides gras,
   et éventuellement
4. d) de 0 à 40% en masse d'au moins un améliorant de combustion,
5. e) de 5 à 20% en masse d'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 hydroxydes, 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
   • * leurs mélanges,
6. f) de 20 à 60% en masse de solvant(s) organique(s) hydrocarboné(s),
7. g) de 0 à 30% en masse d'agent(s) compatibilisant ou co-solvant(s).

According to a first object the invention proposes a liquid fuel additive comprising the mixture:

1. a) from 10 to 50% by weight of at least one phenol or phenol / amine antioxidant, the phenol / amine antioxidant (s) being preferred,
2. b) from 5 to 20% by weight of at least one metal passivator, in particular copper, chosen from amines substituted by triazole groups or by N, N'-disalicylidene groups,
3. c) from 1 to 10% by weight of at least one anti-corrosion agent chosen from fatty acid derivatives,
   and eventually
4. d) from 0 to 40% by weight of at least one combustion improver,
5. e) from 5 to 20% by weight of at least one perfume and / or odor masking and / or re-odorant 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,
   • hydroxides, such as linalool, phenylethyl alcohols,
   • ketones, such as crystallized camphor, ethylmaltol,
   • * essential oils, such as essential oil derived from citrus fruits
   • * their mixtures,
6. f) from 20 to 60% by weight of organic solvent (s) hydrocarbon (s),
7. g) from 0 to 30% by weight of compatibilizing agent (s) or co-solvent (s).

Preferably, the additive further contains a hydrocarbon organic solvent and / or a compatibilizer or co-solvent.

• a) au moins un agent anti-oxydant choisi parmi les molécules contenant au moins un groupement phénol, tel que le di-t-butyl-2,6 méthyl-4 phénol (BHT) et avantageusement une combinaison comprenant au moins un anti-oxydant de type phénolique et un antioxydant dérivé d'une amine ou d'une polyamine éventuellement substituée telle que la dicyclohexyl amine,
• b) au moins un passivateur de métal choisi parmi les amines substituées par des groupements triazoles (benzotriazoles, toluyltriazoles,....) tels que le N, N-bis-(2-éthylhexyl)-4-méthyl-1H-brenzotriazole-1-méthylamine ou par des groupements N,N'-disalicylidène, tels que N,N'-disalicylidène 1,2-diaminopropane,
• c) au moins un agent anti-corrosion choisi parmi les dérivés d'acides gras tels que les esters de dimères d'acides gras et plus particulièrement les esters éthylique de dimères d'acide linoléique et/ou d'acide stéarique, les dérivés acides des anhydrides alkyl succiniques,
  et éventuellement
• e) 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 hydroxydes, 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
  • * 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.

Preferably, the additive comprises:

• a) at least one antioxidant chosen from molecules containing at least one phenol group, such as di-t-butyl-2,6-methyl-4-phenol (BHT) and advantageously a combination comprising at least one antioxidant of phenolic type and a antioxidant derived from an amine or an optionally substituted polyamine such as dicyclohexylamine,
• b) at least one metal passivator chosen from amines substituted with triazole groups (benzotriazoles, toluyltriazoles, ....) such as N, N-bis (2-ethylhexyl) -4-methyl-1H-brenzotriazole; 1-methylamine or by N, N'-disalicylidene groups, such as N, N'-disalicylidene 1,2-diaminopropane,
• c) at least one anti-corrosion agent chosen from fatty acid derivatives such as esters of fatty acid dimers and more particularly ethyl esters of linoleic acid and / or stearic acid dimers, acid derivatives alkyl succinic anhydrides,
  and eventually
• e) 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,
  • hydroxides, 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.

• de 10 à 50 % en masse d'agent(s) anti-oxydant(s),
• de 5 à 20 % en masse de passivateur(s) de métal,
• de 1 à 10 % en masse d'agent(s) anti-corrosion,
• de 5 à 20 % en masse d'agent(s) parfumant(s) et/ou masquant(s) d'odeur et/ou réodorant(s),
• de 20 à 60 % en masse de solvant(s) organique(s) hydrocarboné(s),
• de 0 à 40 % d'améliorant(s) de combustion,
• de 0 à 30 % en masse d'agent(s) compatibilisant ou co-solvant(s).

Preferably, the additive comprises:

• from 10 to 50% by weight of antioxidant (s),
• from 5 to 20% by weight of metal passivator (s),
• from 1 to 10% by weight of anti-corrosion agent (s),
• from 5 to 20% by weight of perfume agent (s) and / or masking (s) of odor and / or re-odor (s),
• from 20 to 60% by weight of organic solvent (s) hydrocarbon (s),
• from 0 to 40% combustion improvers,
• from 0 to 30% by weight of compatibilizing agent (s) or co-solvent (s).

According to a second object the invention provides a method for preparing an additive as defined above, by mixing at room temperature constituents of said additive.

• une majeure partie d'un mélange à base d'hydrocarbures liquides de type Burning Kerosène ou pétrole lampant ayant des températures de distillation comprises entre 180 et 370°C, de préférence entre 180 et 280°C et particulièrement entre 180 et 260 °C; une teneur en composés aromatiques pouvant aller jusqu'à 20%, de préférence inférieure ou égale à 1% ; ces mélanges sont issus de coupes kérosène en général riches en composés aromatiques (benzène, ...) ; ces coupes issues de raffineries pétrolières contiennent en général quelques pourcents de composés aromatiques notamment jusque 20% et peuvent être utilisées comme combustibles liquides ou peuvent être soumises à une désaromatisation ayant pour effet de réduire très fortement la concentration en composés aromatiques (typiquement inférieure ou égale à 1 %) ; ces coupes sont dénommées Burning Kerosene ou pétrole lampant ; les mélanges désaromatisés comme indiqué précédemment ont des propriétés de combustion meilleures que les mélanges plus riches en composés aromatiques ;
• une mineure partie d'au moins un additif tel que défini ci dessus, le mélange à base d'hydrocarbures liquides comprenant des 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.

According to a third object the invention proposes a liquid fuel composition comprising:

• a major part of a mixture based on liquid hydrocarbons of Burning Kerosene type or kerosene having distillation temperatures of between 180 and 370 ° C, preferably between 180 and 280 ° C and particularly between 180 and 260 ° C; an aromatic content of up to 20%, preferably less than or equal to 1%; these mixtures are derived from kerosene cuts in general rich in aromatic compounds (benzene, ...); these cuts from petroleum refineries generally contain a few percent of aromatic compounds including up to 20% and can be used as liquid fuels or may be subject to dearomatization having the effect of greatly reducing the concentration of aromatic compounds (typically less than or equal to 1%); these cuts are called Burning Kerosene or kerosene; the deflavored mixtures as indicated above have better combustion properties than the mixtures which are richer in aromatic compounds;
• a minor portion of at least one additive as defined above, the mixture based on liquid hydrocarbons comprising cuts of the middle distillate types, from refineries and / or agrofuels and / or biofuels and / or biomass and / or synthetic fuels.

Preferably, the composition according to the invention comprises from 250 to 1,000 ppm of additive (s) as defined above.

According to a fourth object the invention proposes the use of a composition as defined above as a fuel for the production of energy, for heating and / or for cooking.

Preferably, the composition according to the invention is used as fuel for heating appliances and in particular for steaming stoves or more preferably as fuel for stoves and in particular for slow-burning stoves.

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION

• une majeure partie d'hydrocarbures liquides ayant des températures de distillation comprises entre 180 et 370°C, de préférence entre 180 et 280 °C et particulièrement entre 180°C et 250°C, notamment du type Burning Kerosene (BUK C1 ou BUK C2) ou pétrole lampant ;
• une mineure partie d'au moins un additif comprenant le mélange
  1. a) d'au moins un agent anti-oxydant de type phénol ou phénol/amine, le ou les anti-oxydants de type phénol/amine étant préféré,
  2. b) d'au moins un passivateur de métal, notamment de cuivre,
  3. c) d'au moins un agent anti-corrosion,
     et éventuellement
  4. d) d'au moins un améliorant de combustion,
  5. e) d'au moins un agent parfumant et/ou masquant d'odeur et/ou réodorant.

The liquid fuel composition comprises:

• a major part of liquid hydrocarbons having distillation temperatures between 180 and 370 ° C, preferably between 180 and 280 ° C and particularly between 180 ° C and 250 ° C, including Burning Kerosene type (BUK C1 or BUK C2 ) or kerosene;
• a minor portion of at least one additive comprising the mixture
  1. a) at least one anti-oxidant agent of phenol or phenol / amine type, the phenol / amine antioxidant (s) being (are) preferred,
  2. b) at least one metal passivator, in particular copper,
  3. c) at least one anti-corrosion agent,
     and eventually
  4. d) at least one combustion improver,
  5. e) at least one perfuming and / or odor-masking and / or re-odoring agent.

Depending on the nature and miscibility of components a) to e) of the additive according to the invention described above with the liquid fuel, the additive may also contain a hydrocarbon organic solvent and optionally a compatibilizer or co-solvent.

As an antioxidant agent of the phenol type, it is possible to use the molecules containing at least one phenol group, molecules which are conventionally used in liquid hydrocarbon compositions for motor fuels or for liquid fuels, such as for example 2,6-di-tert-butyl-4-methylphenol (BHT), their mixtures.

It is advantageous to use combinations comprising at least one phenolic antioxidant and an antioxidant derived from an amine or an optionally substituted polyamine such as dicyclohexylamine, and mixtures thereof.

As a metal passivator, it is possible to use amines substituted with triazole groups (benzotriazoles, toluyltriazoles, ....) such as N, N-bis (2-ethylhexyl) -4-methyl-1H-brenzotriazole. 1-methylamine or by N, N'-disalicylidene groups, such as N, N'-disalicylidene 1,2-diaminopropane, their mixtures.

As an anti-corrosion agent, it is possible to use fatty acid derivatives such as esters of fatty acid dimers and more particularly ethyl esters of linoleic acid and / or stearic acid dimers, derivatives thereof. acids of alkyl succinic anhydrides, their mixtures.

• * les composés tricycliques organiques décrits dans EP 1.591.514 ainsi que
• * les aldéhydes aliphatiques ou aromatiques tels que la vanilline,
• * les esters aliphatiques ou aromatiques, tels que l'acétate de benzyle,
• * les hydroxydes, 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
• * leurs mélanges.

As a scenting agent and / or masking odor and / or reodorant, one can for example quote

• * the organic tricyclic compounds described in EP 1.591.514 as well as
• aliphatic or aromatic aldehydes such as vanillin,
• aliphatic or aromatic esters, such as benzyl acetate,
• hydroxides, such as linalool, phenylethyl alcohols,
• ketones, such as crystallized camphor, ethylmaltol,
• * essential oils, such as essential oil derived from citrus fruits
• * their mixtures.

Advantageously, a mixture of at least one organic tricyclic compound and at least one aldehyde, an ester, a hydroxide, a ketone and an essential oil as defined is advantageously used as a perfume, odor masking or re-odorant. above.

• de 10 à 50 % en masse d'agent(s) anti-oxydant(s),
• de 5 à 20 % en masse de passivateur(s) de métal,
• de 1 à 10 % en masse d'agent(s) anti-corrosion,
• de 5 à 20 % en masse d'agent(s) parfumant(s) et/ou masquant(s) d'odeur et/ou réodorant(s),
• de 20 à 60 % en masse de solvant(s) organique(s) hydrocarboné(s),
• de 0 à 40% d'améliorant(s) de combustion,
• de 0 à 30 % en masse d'agent(s) compatibilisant ou co-solvant(s).

The additive according to the invention advantageously comprises

• from 10 to 50% by weight of antioxidant (s),
• from 5 to 20% by weight of metal passivator (s),
• from 1 to 10% by weight of anti-corrosion agent (s),
• from 5 to 20% by weight of perfume agent (s) and / or masking (s) of odor and / or re-odor (s),
• from 20 to 60% by weight of organic solvent (s) hydrocarbon (s),
• from 0 to 40% combustion improvers,
• from 0 to 30% by weight of compatibilizing agent (s) or co-solvent (s).

The additive according to the invention may be prepared by simple mixing of components a) to e) described above, with the hydrocarbon organic solvent and optionally the compatibilizing agent or co-solvent.

The additive according to the invention has the advantage of being storage stable for at least several months at ambient temperature (-15 to + 40 ° C.) and can therefore be stored in a deposit before mixing with the fuel based on liquid hydrocarbons.

The fuel composition according to the invention generally comprises from 250 to 1,000 ppm of one or more additive (s) according to the invention.

In addition to the usual components of Burning Kerozene, which come mainly from oil refineries, including medium distillate type cuts with the distillation ranges indicated above, liquid hydrocarbons can come from agrofuels, biofuels, biomass and / or synthetic hydrocarbons.

The fuel composition according to the invention can be prepared in a simple manner by incorporating the additive (s) according to the invention by simple physical mixing of the additive or additives and liquid hydrocarbons. It would not be outside the scope of the invention to separately mix the constituents of the additive according to the invention with liquid hydrocarbons.

The hydrocarbon composition according to the invention may contain, in addition to the additive (s) according to the invention, one or more other additives, that is to say different from the constituents a) to e), the solvent and the co- possible solvent of the additive according to the invention.

By way of example of other additives, mention may be made, without limitation, of biocidal additives, additives of filterability limit temperature, additives of cloud point, pour point, lubricity or anti-additives. wear.

Comparative Example 1) - Preparation of additive fuels (Additive A, Additive B), validation on spray stoves

An additive referred to as Additive A is prepared according to the following procedure:

• 10 parties en poids d'antioxydant de type phénol/amine commercialisé sous l'appellation Hitec ® 4235,
• 19 parties en poids d'améliorant de combustion de type ferrocène,
• 6 parties en poids de réodorant (mélange d'aromatiques),
• 5 parties en poids d'éthyle 2 hexanol,
• 60 parties en poids de Solvarex 10 (solvant aromatique lourd commercialisé par Total Fluides).

At room temperature, mix:

• 10 parts by weight of phenol / amine antioxidant sold under the name Hitec® 4235,
• 19 parts by weight of ferrocene type combustion enhancer,
• 6 parts by weight of the resorant (mixture of aromatics),
• 5 parts by weight of ethyl 2 hexanol,
• 60 parts by weight of Solvarex 10 (heavy aromatic solvent marketed by Total Fluides).

At room temperature, 1000 ppm of the Additive A prepared above is mixed with a hydrocarbon composition (equivalent to a BUK C2) which will be referred to hereinafter as BUK C2.

The sulfur content of the BUK C2 is equal to 5 ppm, its density at 15 ° C is 0.8028 g / cm ^3, its specific aromatic content is 20%, its starting point is 184.2 ° C and its end point 253.3 ° C.

Combustion quality: endurance test on a test bench "vaporizing stove"

This test makes it possible to compare the combustion quality of 2 different fuels on spray stoves.

The 2 fuels to be compared run in parallel on two different vaporization stoves, of the same make and model; this in order to obtain comparative results on products having under exactly the same operating conditions.

This comparison is done quantitatively by measuring the mass of unburnt produced during the test in the combustion pots, by each of the two fuels. This amount of deposit is reduced to the weight of fuel consumed.

The duration of this test is 2 weeks, the volume of fuel consumed is about 200 L. Throughout the test, the measurement of flue gas temperature, darkening index and fuel flow allows to follow a possible evolution of the quality of combustion.

BUK C2 / BUK C2 trial + Additive A: analysis of the results

In this test, the performance of the additive A in terms of combustion is evaluated by comparing the virgin BUK C2 with the BUK C2 additive with the additive A.

The quantity of deposits formed is measured: BUK C2 blank: 90 mg / kg BUK C2 + Additive A 40 mg / kg BUK C1 29 mg / kg

An effectiveness of the additive A with respect to the quality of combustion is observed, which results in a smaller amount of deposits formed for the additive BUK. This difference in combustion quality is also observed visually significantly.

• (les caractéristiques du BUK C1 sont les suivantes : teneur en soufre : 5 ppm ; masse volumique à 15°C : 0,8183 g/cm³ ; teneur massique en aromatiques : 0 %, point initial : 185,3°C ; point final : 242,6°C)

The results of the test show that the additive A is effective on the combustion properties of a vaporizer stove by substantially reducing the formation of deposits in the burners. It allows a BUK C2, to achieve the combustion quality of a BUK C1.

• (The characteristics of BUK C1 are as follows: sulfur content: 5 ppm, density at 15 ° C: 0,8183 g / cm ³ , mass content of aromatics: 0%, initial point: 185,3 ° C; final: 242.6 ° C)

Effectiveness of the anti-corrosion agent

The formula of Additive A is complemented by the addition of an anti-corrosion agent whose efficiency is clearly highlighted by the method ASTM D655 copper blade corrosion whose results are reported in the table below. Sample Rating of corrosion BUK C2 OF BUK C2 + Additive A OF BUK C2 + Additive A + anti-corrosion AT

This new formulation is then tested in a vaporizer stove, the respective concentrations of each of the components of the additive package have been adapted to allow an additive treatment rate of 500 ppm.

• A température ambiante, on mélange :
  • 20 parties en poids d'antioxydant de type phénol/amine commercialisé sous l'appellation Hitec ® 4235,
  • 38 parties en poids d'améliorant de combustion de type ferrocène,
  • 12 parties en poids de réodorant,
  • 3,5 parties en poids d'anti-corrosion,
  • 5 parties en poids d'éthyl 2 hexanol,
  • 21,5 parties en poids de Solvarex 10.
• A température ambiante, on mélange 500 ppm de l'Additif B préparé ci-dessus avec une composition d'hydrocarbures commercialisée sous la dénomination Ketrul (équivalent à un BUK C2)
• Un nouveau test permet de comparer du BUK C2 présentant une qualité de combustion dégradée en simulant une pollution par du FOD (Fuel Oil Domestique) (3%) à ce même combustible additivé par l'Additif B.

An additive referred to as Additive B is prepared according to the following procedure:

• At room temperature, mix:
  • 20 parts by weight of phenol / amine antioxidant sold under the name Hitec® 4235,
  • 38 parts by weight of ferrocene type combustion enhancer,
  • 12 parts by weight of the deodorant,
  • 3.5 parts by weight of anti-corrosion,
  • 5 parts by weight of ethyl hexanol,
  • 21.5 parts by weight of Solvarex 10.
• At room temperature, 500 ppm of Additive B prepared above is mixed with a hydrocarbon composition sold under the name Ketrul (equivalent to a BUK C2).
• A new test makes it possible to compare BUK C2 having a deteriorated combustion quality by simulating a pollution by FOD (3%) to this same fuel additive additive B.

$$\mathrm{BUK\; C}2+3\%\mathrm{FOD}//\mathrm{BUK\; C}2+3\%\mathrm{FOD}+\mathrm{Additif\; B}$$

4 tests were carried out on the bench "vaporizing stove": $$\mathrm{BUK\; C}2//\mathrm{BUK\; C}2+3\%\mathrm{FOD}$$

$$\mathrm{BUK\; C}2+3\%\mathrm{FOD}//\mathrm{BUK\; C}2+3\%\mathrm{FOD}+\mathrm{Additive\; B}$$

The amount of deposits formed for BUK C2 is 91 mg / kg and that for BUK C2 + 3% FOD is 300 mg / kg.

It is noted that the pollution by FOD greatly degrades the quality of combustion and causes a significant variation in the amount of deposits formed.

Impact of Additivation by Additive B.

While the amount of deposits formed for BUK C2 + 3% FOD is 300 mg / kg, it is only 17 mg / kg for BUK C2 + 3% FOD + 500 ppm Additive B.

These results highlight the very good effectiveness of Additive B, which significantly improves the quality of combustion.

The additive as described above (Additive A, Additive B) significantly improves the quality of combustion on thermal appliances such as spray stoves by greatly reducing the amount of deposits formed.

This additivation makes it possible in particular for a BUK class C2 to have a combustion quality equivalent to that of a BUK C1, even when it is polluted with FOD up to contents of 3%. The addition of anti-corrosion agent in the specific formulation does not change this result.

Example 2 - Preparation of Fuels According to the Invention (Containing Additive C or Additive D), Slow Cooking Range Tests.

• un dépôt de carbone important au fond du pot de combustion,
• des dépôts ressemblant à du cuivre sur les mèches.

Additive B is evaluated by an endurance test on a slow-burning stove of the AGA® type. After 6 weeks of testing, we observe the appearance of a marked noise, and the safety of the device. Visual inspection of the first device after shutdown shows:

• a large carbon deposit at the bottom of the burnpot,
• deposits resembling copper on the locks.

If the additive B is quite efficient for the combustion of the vaporizing stoves as shown in the results of Example 1, it is not satisfactory for slow combustion stoves.

Impact of Copper on Combustion Spray Stove

In order to simulate a copper contamination which could come in particular from certain types of copper-based pipe, a test is carried out for quantify the formation of deposits after bench stove test for BUK C2 containing 2 or 10 ppm copper.

This test is shot in small pace to make more severe operating conditions.

The quantities of deposits formed are measured: BUK C2 virgin 155 mg / kg BUK C2 + Additive B 11 mg / kg BUK C2 + Additive B + 2 ppm copper 70 mg / kg BUK C2 + Additive B + 10 ppm copper 215 mg / kg

Conclusion:

From a certain grade, it can be seen that copper has a direct impact on the quality of combustion and thus on the formation of deposits. In addition, visual observation of the burn pots highlights the impact of copper on the deposition formation at the fuel supply port.

An additive according to the invention called Additive C is tested on endurance test on slow-burning stove.

• A température ambiante, on mélange :
  • 20 parties en poids d'anti-oxydant phénol/amine commercialisé sous l'appellation Hitec 4235,
  • 8 parties en poids passivateur du cuivre de type benzotriazole,
  • 3,5 parties en poids d'anti-corrosion (mélange d'esters de dimères d'acides oléique et d'acide stéarique),
  • 12 parties en poids d'agent réodorant,
  • 35 parties en poids d'améliorant de combustion type ferrocène,
  • 11,5 parties en poids de Solvarex 10 (solvant organique aromatique lourd) commercialisé par la demanderesse,
  • 10 parties en poids d'éthyl-2 hexanol (agent compatibilisant)
• A température ambiante, on mélange 500 ppm de l'Additif C avec une composition d'hydrocarbures commercialisée sous la dénomination Ketrul (équivalent à un BUK C2)
• Les résultats de l'essai montrent une nette amélioration par rapport à l'essai précédent avec l'Additif B : l'essai a pu tourner sans arrêt pendant au moins 6 mois, ce qui n'était pas le cas avec l'Additif B.

Additive C is prepared as follows:

• At room temperature, mix:
  • 20 parts by weight of phenol / amine antioxidant sold under the name Hitec 4235,
  • 8 parts by weight passivator of benzotriazole copper,
  • 3.5 parts by weight of anti-corrosion (mixture of esters of oleic acid and stearic acid dimers),
  • 12 parts by weight of the deodorant agent,
  • 35 parts by weight of ferrocene type combustion enhancer,
  • 11.5 parts by weight of Solvarex 10 (heavy aromatic organic solvent) marketed by the Applicant,
  • 10 parts by weight of 2-ethyl hexanol (compatibilizing agent)
• At ambient temperature, 500 ppm of Additive C is mixed with a hydrocarbon composition sold under the name Ketrul (equivalent to a BUK C2).
• The results of the test show a clear improvement over the previous test with Additive B: the test was able to run continuously for at least 6 months, which was not the case with Additive B .

In addition, there is the presence of bright deposit having the appearance of copper deposition much less than for BUK C2 additive with Additive B and a large decrease in the amount of carbon deposits.

As the endurance test on a slow-burning stove is quite cumbersome (minimum duration of 6 months), laboratory methods that best simulate the constraints of this test have been developed by the applicant to propose an optimization. of Additive C and are detailed below.

Thermal stability - Interaction with copper

Different additive formulations were tested by adapting two methods:

a / Method derived from ASTM D130

The test consists of a copper blade corrosion test at 100 ° C for 48 hours; the copper content in the different virgin or additive BUK solutions is measured at the end of the test and the appearance of the solutions is observed.

b / Method derived from ASTM D570

The formulations are aged in the presence of copper or iron (dissolved in the form of wire), at 105 ° for 48 hours, then the existing and adherent gums are quantified in the usual way.

• de la nature chimique de l'antioxydant et du taux d'additivation pour ce composé,
• de la nature chimique du passivateur de cuivre et du taux d'additivation pour ce composé,

sur la stabilité thermique qui est un paramètre très important sur les cuisinières à combustion lente.These 2 test methods aim to study the influence:

• the chemical nature of the antioxidant and the rate of additivation for this compound,
• the chemical nature of the copper passivator and the additive rate for this compound,

on thermal stability which is a very important parameter on slow combustion stoves.

Test Results: Method Derived from ASTM D130

• Additif D = Additif C avec double dose de passivateur de cuivre et diminution du taux d'améliorant de combustion
• Additif E = Additif C avec changement de passivateur de cuivre à dosage équivalent
• Additif F=Additif C avec changement de passivateur de cuivre à double dose
• Additif G = Additif C avec augmentation du dosage de l'antioxydant et diminution du dosage de l'améliorant de combustion
• Additif H = Additif C avec changement d'antioxydant (mélange phénols amines, avec une plus grande concentration en produits aminés)

A matrix of products is tested by both methods:

• Additive D = Additive C with a double dose of copper passivator and a decrease in the rate of combustion enhancer
• Additive E = Additive C with change of copper passivator at equivalent dosage
• Additive F = Additive C with change of copper passivator at double dose
• Additive G = Additive C with increased dosage of the antioxidant and decreased dosage of the combustion improver
• Additive H = Additive C with change of antioxidant (mixture phenols amines, with a higher concentration of amino products)

In the table below the copper contents and the appearance of the fuel mixture + additive "" are indicated. Product Copper content Aspect BUK C2 virgin 0.05 ppm Clear and clear solution BUK C2 + Additive C <0.05 ppm Slightly yellow solution BUK C2 + Additive D <0.05 ppm Slightly yellow solution BUK C2 + Additive E 0.8 ppm Solution less clear, presence of deposits BUK C2 + Additive F 1.10 ppm Brown solution presence of deposits BUK C2 + Additive G 0.25 ppm Very slightly yellow solution BUK C2 + Additive H 1.90 ppm Clear and clear solution

Conclusion

It is found that the choice of antioxidant and copper passivator has a significant impact on thermal stability.

Test Results: Method Derived from ASTM D570

• Additive B '= Additive C without copper passivator
• Additive C '= Additive C with change of antioxidant: phenol / amine mixture with a higher concentration of amine products
• Additive D = Additive C without combustion enhancer
• Additive E '= additive C without combustion enhancer and without copper passivator
• Additive F '= Additive C with change of antioxidant for a phenol amine mixture with a higher concentration of amine products
• Additive G '= Additive C with change of antioxidant for a phenol amine mixture with greater concentration of amine products, without improving combustion.

Test in the presence of copper Composition Cu content after oxidation (ppm) Color after oxidation Total GP. (Mg / 100mL) BUK blank 0.15 5 0.5 BUK + C 0.20 4 0.8 BUK + B ' 0.65 -5 1.7 BUK + C ' 1.05 9 0.4 BUK + D ' 0.10 13 0.3 BUK + E ' 0.75 -4 1.0 BUK + F ' 0.65 -8 1.4 BUK + G ' <0.6 3 0.4

These results confirm the effectiveness of the copper passivator (Additive C compared to Additive B ') as well as the better performance of the antioxidant 2 (phenol / amine type with greater concentration of amino products) than the anti -oxidant 1 (phenol / amine type) (Additive C compared to Additive C 'or Additive G'). <u> Results of the test in the presence of iron </ u> Composition Total GP. (Mg / 100mL) BUK blank 0.1 BUK + C 1.5 BUK + B ' 0.8 BUK + C ' 0.9 BUK + D ' 0.1 BUK + E ' 0.1 BUK + F ' 0.1 BUK + G ' 0.1

Conclusion

These results demonstrate that if the combustion improver acts as a combustion catalyst, it brings iron into the final solution which greatly degrades the thermal stability of this solution.

• A température ambiante, on mélange :
  • 30 parties en poids d'anti-oxydant de type phénol/amine avec plus grande concentration en produits aminés que l'anti-oxydant de l'Additif C,
  • 8 parties en poids de passivateur du cuivre de type benzotriazole,
  • 3,5 parties en poids d'anti-corrosion (mélange d'esters de dimères d'acides linoléique et d'acide stéarique),
  • 12 parties en poids d'agent réodorant,
  • 36,5 parties en poids de Solvarex 10(solvant organique aromatique) commercialisé par la demanderesse,
  • 10 parties en poids d'éthyl-2 hexanol (agent compatibilisant)

Another additive according to the invention called Additive D is prepared as follows:

• At room temperature, mix:
  • 30 parts by weight of phenol / amine antioxidant with higher concentration of amine products than the antioxidant of Additive C,
  • 8 parts by weight of benzotriazole copper passivator,
  • 3.5 parts by weight of anti-corrosion (mixture of linoleic acid dimer esters and stearic acid),
  • 12 parts by weight of the deodorant agent,
  • 36.5 parts by weight of Solvarex 10 (aromatic organic solvent) marketed by the Applicant,
  • 10 parts by weight of 2-ethyl hexanol (compatibilizing agent)

Additive D is tested in a long-term laboratory test (for several months) and on AGA® type slow combustion stoves by mixing 500 ppm of Additive D with BUK C2.

Throughout the period of operation, the fuel thus additive has given full satisfaction and has significantly increased the maintenance period of this type of thermal equipment.

Claims (14)

1. Additive for Burning Kerosene or Domestic Kerosene type liquid fuel comprising the mixture:

   a) from 10 to 50% by mass of at least one antioxidant of the phenol or phenol/amine type,

   b) from 5 to 20% by mass of at least one metal passivator selected from amines substituted by triazole groups or by N,N'-disalicylidene groups,

   c) from 1 to 10% by mass of at least one corrosion inhibitor selected from fatty acid derivatives,
   and optionally

   d) from 0 to 40% by mass of at least one combustion improver,

   e) from 5 to 20% by mass of at least one perfuming and/or odour-masking and/or reodorizing agent selected from

   * the organic tricyclic compounds of formula (I) below

   

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

   * aliphatic or aromatic aldehydes,

   * aliphatic or aromatic esters,

   * hydroxides,

   * ketones,

   * essential oils,

   * mixtures thereof,

   f) from 20 to 60% by mass of organic hydrocarbon-containing solvent(s).

   g) from 0 to 30% by mass of compatibilizing agent(s) or co-solvent(s).
2. Additive according to claim 1 in which the antioxidant or antioxidants are of the phenol/amine type.
3. Additive according to claim 1 or 2, comprising

   a) at least one antioxidant selected from a combination comprising at least one antioxidant of the phenolic type and one antioxidant derived from an optionally substituted amine or polyamine,

   b) at least one metal passivator selected from N, N-bis-(2-ethylhexyl)-4-methyl-1H-benzotriazo le-1-methylamine or N,N'-disalicylidene 1,2-diaminopropane,

   c) at least one corrosion inhibitor selected from the esters of fatty acid dimers and more particularly the ethyl esters of linoleic acid and/or stearic acid dimers, acid derivatives of alkyl succinic anhydrides,
   and optionally

   e) at least one perfuming and/or odour-masking agent and/or reodorizing agent, selected from the mixture of at least one organic tricyclic compound and of at least an aldehyde, an ester, a hydroxide, a ketone, and an essential oil.
4. Additive according to one of claims 1 to 4 in which the aliphatic or aromatic aldehyde is vanillin, the aliphatic or aromatic ester is benzyl acetate, the hydroxide is linalol or a phenylethyl alcohol, the ketone is crystallized camphor or ethylmaltol, and the essential oil is essential oil derived from citrus fruits.
5. Preparation process of an additive as defined in any one of claims 1 to 4, by mixing the components of said additive at ambient temperature.
6. Liquid fuel composition comprising

   - a major part of a liquid hydrocarbon-based mixture of the Burning Kerosene or domestic kerosene type having distillation temperatures comprised between 180 and 370°C, a content of aromatic compounds which can range up to 20%,

   - a minor part of at least one additive as defined in any one of claims 1 to 4,

   the liquid hydrocarbon-based mixture comprising cuts of middle distillate types, originating from refineries and/or agrofuels and/or biofuels and/or biomass and/or synthetic fuels.
7. Liquid fuel composition according to claim 6 in which the mixture of liquid hydrocarbons of the Burning Kerosene or domestic kerosene type has distillation temperatures comprised between 180 and 280°C.
8. Liquid fuel composition according to claim 6 or 7 in which the mixture of liquid hydrocarbons of the Burning Kerosene or domestic kerosene type has a content of aromatic compounds less than or equal to 1%.
9. Composition according to one of claims 6 to 8 comprising from 250 to 1,000 ppm of additive(s) as defined in any one of claims 1 to 4.
10. Use of a composition as defined in one of claims 6 to 9 as fuel for the production of energy, for heating and/or for cooking.
11. Use of a composition according to claim 10 as fuel for heating devices.
12. Use of a composition according to claim 11 in which the heating device is a vaporizing stove.
13. Use of a composition according to claim 10 as fuel for ranges.
14. Use of a composition according to claim 13 in which the range is a slow combustion range.