US20150315506A1 - Additives for improving the resistance to wear and lacquering of vehicle fuels of the gas oil or bio gas oil type - Google Patents

Additives for improving the resistance to wear and lacquering of vehicle fuels of the gas oil or bio gas oil type Download PDF

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US20150315506A1
US20150315506A1 US14/421,628 US201314421628A US2015315506A1 US 20150315506 A1 US20150315506 A1 US 20150315506A1 US 201314421628 A US201314421628 A US 201314421628A US 2015315506 A1 US2015315506 A1 US 2015315506A1
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additives
gas oil
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Thomas Dubois
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TotalEnergies Marketing Services SA
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Total Marketing Services SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0259—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

  • a subject of the present invention is additives making it possible to limit the formation of soaps and/or varnishes in the internal parts of the injection systems of engines for (bio)gas oil type vehicle fuels, i.e. in particular to increase their resistance to lacquering.
  • Gas oil or diesel is a vehicle fuel for diesel engines (compression engines) comprising middle distillates with a boiling point comprised between 100 and 500° C.
  • a gas oil can be constituted by a mixture of middle distillates of fossil origin and biofuels.
  • biofuel is meant the vehicle fuels obtained from organic matter (biomass), as opposed to the vehicle fuels originating from fossil resources.
  • biogas oils or also called biodiesel
  • alcohols there can be mentioned, as examples of known biofuels, the bio gas oils (or also called biodiesel) and the alcohols.
  • Biodiesel or bio gas oil is an alternative to standard vehicle fuel for diesel engines.
  • This biofuel is obtained from vegetable or animal oil (including used cooking oils) converted by a chemical process called transesterification causing this oil to react with an alcohol in order to obtain fatty acid esters.
  • transesterification causing this oil to react with an alcohol in order to obtain fatty acid esters.
  • fatty acid methyl esters (FAMEs) and fatty acid ethyl esters (FAEEs) are obtained respectively.
  • B Mixtures of middle distillates of fossil origin and bio gas oil are denoted by the letter “B” followed by a number indicating the percentage of bio gas oil contained in the gas oil.
  • B99 contains 99% bio gas oil and 1% middle distillates of fossil origin
  • B20 contains 20% bio gas oil and 80% middle distillates of fossil origin etc.
  • Gas oil vehicle fuels of the B0 type which do not contain oxygen-containing compounds are therefore distinguished from bio gas oil vehicle fuels of the Bx type which contain x % (v/v) vegetable oil esters or fatty acid esters, most often methyl esters (FAME or VOME).
  • bio gas oil is used alone in the engines, the vehicle fuel is denoted by the term B100.
  • bio gas oil is used to identify the B0 or Bx type vehicle fuels for diesel engines (compression engines).
  • gas oil or diesel vehicle fuel bases for example hydrotreatment methods
  • gas oil or diesel vehicle fuels having a low (less than 100 ppm) or even very low sulphur content have a reduced ability to lubricate the engine fuel injection system, which results for example in early failure of the engine fuel injection pump during the lifetime of the engine, failure occurring for example in high-pressure vehicle fuel injection systems, such as high-pressure rotary distributors, in-line pumps and combined pump-injector units.
  • higher-grade vehicle fuel of the gas oil or bio gas oil type is meant any gas oil or bio gas oil vehicle fuel to which at least 50 ppm by mass of deposit reducing and/or detergent and/or dispersant additives have been added.
  • FIG. 1 is a photograph of a diesel engine injector with high-pressure direct injection
  • FIG. 2 is a photograph of a needle of a diesel engine injector with direct injection, fouled with soap and/or varnish type deposits (“lacquering”);
  • FIG. 3 is a photograph of a nozzle of a diesel engine injector with indirect injection, fouled with coking type deposits.
  • FIG. 4 is a photograph of a needle of a diesel engine injector with direct injection, fouled with soap and/or varnish type deposits (“lacquering”).
  • the lacquering phenomenon does not relate to the deposits which are present on the outside of the injection system 5 or 5 ′ ( FIGS. 1 and 3 ) and which are associated with coking which gives rise to fouling and partial or total blocking of the injection nozzles 4 or 4 ′ (nozzle “coking” or “fouling”). Lacquering and coking are two phenomena clearly distinguished by:
  • the deposits 5 ′ formed are characterized in that they are constituted by pyrolysis of the hydrocarbons entering the combustion chamber and have the appearance of carbonaceous deposits.
  • the coking tendency is much less marked. This coking is simulated in the CEC F098-08 DW10B standard engine test, in particular when the vehicle fuel tested is contaminated with metallic zinc.
  • the injection of the vehicle fuel is not carried out directly in the combustion chamber as in the case of direct injection engines.
  • the pressure and the temperature in a prechamber are below those of a combustion chamber of direct injection engines.
  • the pyrolysis of the vehicle fuel produces carbonaceous particles which are deposited on the surface of the nozzles 4 ′ of the injectors (“throttling diesel nozzle”) and block the apertures 6 of the nozzles 4 ′ ( FIG. 3 ). Only the surfaces of the nozzle 4 ′ exposed to the combustion gases are at risk of carbon deposits (coking). In terms of performance, the phenomenon of coking causes a loss of engine power.
  • Lacquering is a phenomenon that appears only in direct injection diesel engines and only occurs upstream of the combustion chamber, i.e. in the injection system.
  • the injectors 3 of direct injection diesel engines comprise a needle 2 the lift of which allows precise control of the quantity of fuel injected at high pressure directly into the combustion chamber.
  • the lacquering causes the appearance of deposits 1 which appear specifically at the level of the needles 2 of the injectors 3 ( FIGS. 1 and 2 ).
  • the lacquering phenomenon is linked to the formation of soap and/or varnish in the internal parts of the injection systems of engines for (bio) gas oil type fuels.
  • the lacquering deposit 1 can be located on the end 4 of the needles 2 of the injectors 3 , both on the head and on the body of the needles 2 of the vehicle fuel injection system but also throughout the entire needle lift control system (valves not shown) of the injection system. This phenomenon is particularly marked in the case of engines using higher-grade (bio) gas oil vehicle fuels. When these deposits are present in large quantities, the mobility of the needle 2 of the injector 3 fouled with these deposits 1 is compromised. This lacquering phenomenon can eventually generate a loss of flow rate of vehicle fuel injected and therefore a loss of engine power.
  • lacquering can also cause an increase in engine noise and sometimes starting problems. Indeed, the parts of the needles 2 fouled by the deposits of soap and/or varnish 1 can adhere to the internal walls of the injector 3 . The needles 2 are then blocked and the fuel can no longer pass through.
  • Another possible source of sodium can be from the corrosion inhibitors used when petroleum products are conveyed in certain pipes, such as sodium nitrite;
  • the present invention proposes additives with preventive and curative effects, making it possible to limit the soap and/or varnish deposits in the internal parts of the injection systems, i.e. to improve resistance to the phenomenon of lacquering in engines using higher-grade (bio) gas oil and/or (bio) diesel type vehicle fuels, the sulphur content of which is less than or equal to 500 ppm by mass, and which comprise at least 50 ppm by mass of deposit reducer(s) and/or detergents and/or dispersant(s).
  • These additives therefore prevent these deposits to form (preventive), and allow when they are formed, to be removed by render the injectors cleaner (curative).
  • At least one additive which comprises at least 50% by mass of partial polyol ester(s), said polyol esters comprising x ester units, y hydroxylated units and z ether units, x, y and z being integers such that x varies from 1 to 10, y varies from 1 to 10, and z varies from 0 to 6, preferably x varies from 1 to 10, y varies from 3 to 10, and z varies from 0 to 6.
  • partial polyol esters are known per se; they can for example be prepared by esterification of fatty acid(s) and linear and/or branched polyols optionally comprising (hetero)cycles of 5 to 6 atoms bearing hydroxyl functions.
  • the product(s) originating from this esterification reaction comprise(s) a distribution of ester units, hydroxylated units and ether units such that x varies from 1 to 4, y varies from 1 to 7 and z varies from 1 to 3.
  • this type of synthesis leads to a mixture of mono-, di-, tri- and optionally tetra-esters as well as small quantities of fatty acid(s) and polyols which have not reacted.
  • the polyol esters are obtained by esterification of fatty acid(s) and of linear and/or branched polyols optionally comprising heterocycles of 4 to 5 carbon atoms and an oxygen atom, bearing hydroxyl functions.
  • the polyols will be chosen from the linear polyols comprising more than three hydroxyl functions and the polyols comprising at least one (hetero)cycle of 5 or 6 atoms, preferably heterocycles of 4 to 5 carbon atoms and an oxygen atom, optionally substituted by hydroxyl groups, these polyols being able to be used alone or in a mixture.
  • these polyols are referenced R in the formulations mentioned below.
  • the polyols with linear or branched hydrocarbon chains comprise at least four units represented in formula (I) below:
  • the polyols with linear or branched hydrocarbon chains comprise at least four units represented in formula (II) below:
  • R1 and R2 are identical or different and represent either the hydrogen atom, or a —CH 3 or —C 2 H 5 group or a —CH 2 —OH group.
  • polyols R some comprise at least one (hetero)cycle of 4 or 5 carbon atoms and an oxygen atom, optionally substituted by hydroxyl groups and correspond to general formula (III) below:
  • s and t being integers, and when s is equal to 1, t is equal to 3 and when s is zero, t is equal to 4.
  • some comprise at least two heterocycles of 4 or 5 carbon atoms and one oxygen atom connected by the formation of an acetal bond between a hydroxyl function of each ring, those heterocycles being optionally substituted by hydroxyl groups.
  • the polyols are chosen from the group comprising erythritol, xylitol, D-arabitol, L-arabitol, ribitol, sorbitol, malitol, isomalitol, lactitol, sorbitan, volemitol, mannitol, pentaerythritol, 2-hydroxymethyl-1,3-propanediol, 1,1,1-tri(hydroxymethyl)ethane, trimethylolpropane and carbohydrates such as sucrose, fructose, maltose, glucose and saccharose, preferably sorbitan.
  • the partial polyol esters are chosen from the partial sorbitan esters, preferably sorbitan monooleate, used alone or in a mixture.
  • the fatty acids from which the esters according to the invention originate can be chosen from the fatty acids the chain length of which varies from 10 to 24 carbon atoms and/or at least one diacid substituted by at least one polymer, for example poly(iso)butene comprising from 8 to 100 carbon atoms.
  • the fatty acids can originate from the transesterification or the saponification of vegetable oils and/or animal fats.
  • the preferred vegetable oils and/or animal fats are chosen according to their oleic acid concentration.
  • the fatty acids can also originate from tall oil fatty acids which comprise a majority of fatty acids, typically greater than or equal to 90% by mass as well as resin acids and unsaponifiables in a minority, i.e. in quantities generally less than 10%.
  • Preferred additives according to the invention capable of improving the lacquering resistance of higher-grade (bio)diesel vehicle fuels comprise partial sorbitan esters.
  • Other preferred additives comprise at least 50% by mass of mono- and/or diester(s) of isobutylenesuccinic acid and polyols according to one of formulae I to III.
  • Other preferred additives comprise at least 50% by mass of mono- and/or diester(s) of monocarboxylic acids with 12 to 24 carbon atoms and polyols according to one of formulae I to III.
  • the invention also relates to an additive package for (bio) gas oil vehicle fuels containing at least one lacquering resistance additive as defined previously and at least one or more other functional additives, such as deposit reducers/dispersants, anti-oxidants, combustion improvers, corrosion inhibitors, low temperature performance additives (improving the cloud point, sedimentation rate, filterability and/or low temperature flow), colorants, emulsion breakers, metal deactivators, anti-foaming agents, agents improving the cetane number, compatibilizing agents, lubricity additives, anti-wear agents and/or friction modifiers, and one or more solvents or co-solvents.
  • functional additives such as deposit reducers/dispersants, anti-oxidants, combustion improvers, corrosion inhibitors, low temperature performance additives (improving the cloud point, sedimentation rate, filterability and/or low temperature flow), colorants, emulsion breakers, metal deactivators, anti-foaming agents, agents improving the cetane number, compatibilizing agents, lubricity additives
  • the use of the additives according to the invention makes it possible to improve the lacquering resistance at the level of the fuel injectors, and thus limit the formation (the deposit) of soap and/or varnish in the presence of the additives such as the deposit reducers and/or detergent and/or dispersants.
  • the use of these additives in (bio) gas oil vehicle fuels makes it possible to reduce the blockage rate and deterioration in the fuel admission or injection system, in particular on the injection pump.
  • the bio gas oil vehicle fuels can comprise middle distillates having a boiling point comprised between 100 and 500° C.; their incipient crystallization temperature ICT is often above or equal to ⁇ 20° C., in general comprised between ⁇ 15° C. and +10° C.
  • These distillates are mixtures of bases that can be selected for example from the distillates obtained by direct distillation of gasoline or crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates originating from the catalytic cracking and/or hydrocracking of vacuum distillates, the distillates resulting from ARDS (atmospheric residue desulphurization) type conversion processes and/or visbreaking.
  • the (bio) gas oil vehicle fuels can also contain light cuts such as the gasolines originating from distillation, catalytic or thermal cracking units, alkylation, isomerization, desulphurization units and steam cracking units.
  • the (bio) gas oil vehicle fuels can contain novel sources of distillates, among which there can be mentioned in particular:
  • alcohols such as methanol, ethanol, butanols, ethers, (MTBE, ETBE, etc) in general used in a mixture with the gasoline vehicle fuels, but sometimes with heavier vehicle fuels of the gas oil type,
  • oils and/or their esters such as vegetable oil or fatty acid methyl or ethyl esters (VOME, FAME, VOEE, FAEE),
  • hydrotreated and/or hydrocracked and/or hydrodeoxygenated (HDO) vegetable and/or animal oils are hydrotreated and/or hydrocracked and/or hydrodeoxygenated (HDO) vegetable and/or animal oils,
  • vehicle fuel and fuel bases can be used alone or in a mixture with conventional petroleum middle distillates as vehicle fuel base(s); they generally comprise paraffin long chains greater than or equal to 10 carbon atoms, preferably from C 14 to C 30 .
  • the (bio) gas oil vehicle fuels have a sulphur content less than or equal to 500 ppm by mass, advantageously less than or equal to 100 ppm by mass, and capable of being reduced to a content less than or equal to 50 ppm by mass, or even less than or equal to 10 ppm by mass (this is the case of diesel fuels for current vehicles for which the sulphur content according to European standard EN 590 currently in force must be less than or equal to 10 ppm by mass).
  • the additives providing resistance to lacquering, i.e. to the formation of soap and/or varnish in the internal parts of the injection systems of engines for (bio) gas oil vehicle fuels according to the invention can be incorporated in the vehicle fuels up to a value of 10% by mass.
  • the concentration of partial esters according to the invention in the final vehicle fuel is comprised between 20 and 1000 ppm by mass and advantageously between 30 and 200 ppm by mass, i.e. ppm by mass relative to the total mass of the vehicle fuel with additives.
  • the higher-grade (bio) gas oil compositions contain at least 20 ppm by mass of at least one additive according to the invention and optionally at least one or more other functional additives.
  • concentration of additives according to the invention in the composition i.e. the concentration of partial ester can vary from 20 to 1000 ppm by mass, and more particularly from 30 to 200 ppm by mass m/m.
  • the lacquering resistance additives of the present invention can be used alone or in a mixture with deposit reducers and/or detergents and/or dispersants, anti-oxidants, combustion improvers, corrosion inhibitors, low temperature performance additives (improving the cloud point, sedimentation rate, filterability and/or low temperature flow), colorants, emulsion breakers, metal deactivators, anti-foaming agents, agents improving the cetane number, anti-wear and lubricity additives and/or friction modifiers, co-solvents, compatibilizing agents etc.
  • the other functional additive(s) can be chosen non-limitatively from:
  • the optional other additives are generally incorporated in quantities varying from 50 to 1500 ppm m/m, i.e. ppm by mass relative to the total mass of the vehicle fuel with additives.
  • additives can be incorporated into the fuels following any known method; by way of example, the additive or the mixture of additives can be incorporated in concentrate form comprising the additive(s) and a solvent, compatible with the (bio) diesel fuel, the additive being dispersed or dissolved in the solvent.
  • concentrates in general contain from 20 to 95% by mass of solvents.
  • concentration of additives according to the invention as a function of any dilution of the additive in a solvent, the possible presence of other components originating for example from the esterification reaction and/or other functional additives incorporated in the final vehicle fuel.
  • the solvents are organic solvents that generally contain hydrocarbon solvents.
  • solvents there can be mentioned petroleum fractions, such as naphtha, kerosene, heating oil; aliphatic and/or aromatic hydrocarbons such as hexane, pentane, decane, pentadecane, toluene, xylene, and/or ethylbenzene and alkoxyalkanols such as 2-butoxyethanol and/or mixtures of hydrocarbons such as mixtures of commercial solvents such as for example Solvarex 10, Solvarex LN, Solvent Naphtha, Shellsol AB, Shellsol D, Solvesso 150, Solvesso 150 ND, Solvesso 200, Exxsol, ISOPAR and optionally co-solvents or combatibilizing agents, such as 2-ethylhexanol, decanol, isodecanol and/or isotridecanol.
  • solvents there can be mentioned petroleum fractions, such as naphtha, kerosene, heating oil; aliphatic
  • the invention relates to the use of at least one additive composition according to the invention incorporated in a vehicle fuel of the higher-grade (bio) gas oil type for improving the resistance to lacquering, i.e. fouling on the head and/or on the body of the needles of the fuel injection system but also in the whole needle lift control system (valves) of the injection system, in particular for engines provided with high-pressure direct fuel injection systems, with which most vehicles complying with the Euro 3 and more recent regulations are equipped.
  • a vehicle fuel of the higher-grade (bio) gas oil type for improving the resistance to lacquering, i.e. fouling on the head and/or on the body of the needles of the fuel injection system but also in the whole needle lift control system (valves) of the injection system, in particular for engines provided with high-pressure direct fuel injection systems, with which most vehicles complying with the Euro 3 and more recent regulations are equipped.
  • the subject of the present invention also relates to the use of a composition of (bio) gas oil vehicle fuel as described above, in order to limit the soap and/or varnish deposits in the internal parts of the injection systems of the engines using said composition, preferably direct injection engines, in particular high-pressure direct injection engines.
  • a composition of (bio) gas oil vehicle fuel as described above, in order to limit the soap and/or varnish deposits in the internal parts of the injection systems of the engines using said composition, preferably direct injection engines, in particular high-pressure direct injection engines.
  • the subject of the present invention also relates to a process for limiting the soap and/or varnish deposits in internal parts of the injection system of an engine for (bio) gas oil vehicle fuels (diesel engines) having a sulphur content less than or equal to 500 ppm by mass, said process comprising the combustion in said engine of a (bio) gas oil vehicle fuel composition as defined above.
  • the process applies to direct injection engines, in particular high-pressure direct injection engines.
  • the process according to the invention avoids and prevents the formation of deposits of soap and/or varnish in the internal parts of the injection system of the engine, in order to keep said engine clean.
  • the process according to the present invention removes the soap and/or varnish deposited in the internal parts of the injection system of the engine, for a curative action, cleaning up the engine.
  • the engine used is a four-cylinder, 16-valve, high-pressure injection common rail diesel engine with a cylinder capacity of 1500 cm 3 and a power of 80 hp: regulation of the fuel injection pressure takes place in the high-pressure part of the pump.
  • the power point is used over a period of 40 h at 4000 rpm; the position of the injector in the chamber has been lowered by 1 mm relative to its nominal position, which on the one hand promotes the release of thermal energy from combustion, and on the other hand brings the injector closer to the combustion chamber.
  • the flow rate of vehicle fuel injected is adjusted so as to obtain an exhaust temperature of 750° C. at the start of the test.
  • the injection advance was increased by 1.5° crankshaft relative to the nominal setting (changing from +12.5° to +14° crankshaft) still with the aim of increasing thermal stresses to which the injector nozzle is subjected.
  • the injection pressure was increased by 10 MPa relative to the nominal pressure (i.e. changing from 140 MPa to 150 MPa) and the temperature is set at 65° C. at the inlet of the high-pressure pump.
  • the technology used for the injectors requires a high fuel return, which promotes degradation of the vehicle fuel since it can be subjected to several cycles in the high-pressure pump and the high-pressure chamber before being injected into the combustion chamber.
  • a variant of the method for testing the clean-up effect i.e. cleaning of type 1 and/or type 2 deposits
  • cleaning of type 1 and/or type 2 deposits has also been developed. It is based on the preceding method but is separated into two 20 hour periods:
  • a higher-grade gas oil B7 (containing detergent of the PIBSI type and an acid product) known for its tendency to cause lacquering.
  • two of the four injectors are dismantled and assessed in order to verify the quantity of deposits present and then replaced by two new injectors.
  • the product to be assessed is used.
  • the injectors are dismantled and assessed.
  • Set 1 2 injectors having undergone 20 hours of higher-grade vehicle fuel known for its tendency to cause lacquering.
  • the smoke values allow the combustion timing to be monitored at the start of the test (target value 3FSN) and ensure that it is properly repeatable from one test to the next.
  • the injectors are dismantled at the end of the test in order to inspect and assess the deposits formed along the needles.
  • the procedure adopted for assessing the needles is as follows:
  • the scale of scores varies from ⁇ 2.5 (for a heavy deposit) to 10 (for a new needle without any deposit).
  • the final score is a weighted average of the scores over all the assessed surfaces of the needle, i.e. the conical part and the body or cylindrical part of the needle.
  • the cylindrical zone (directly following the conical part) represents 68% of the overall assessment of the needle and the conical zone represents 32% of the overall assessment of the needle.
  • each of these two zones is divided into 4.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubricants (AREA)
US14/421,628 2012-08-22 2013-08-20 Additives for improving the resistance to wear and lacquering of vehicle fuels of the gas oil or bio gas oil type Abandoned US20150315506A1 (en)

Applications Claiming Priority (3)

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FRFR1257939 2012-08-22
FR1257939A FR2994695B1 (fr) 2012-08-22 2012-08-22 Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole
PCT/EP2013/067311 WO2014029770A1 (fr) 2012-08-22 2013-08-20 Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole

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AR (1) AR092373A1 (zh)
BR (1) BR112015003674A2 (zh)
EA (1) EA031490B1 (zh)
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US10767126B2 (en) 2016-10-21 2020-09-08 Total Marketing Services Combination of fuel additives
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US10767126B2 (en) 2016-10-21 2020-09-08 Total Marketing Services Combination of fuel additives
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FR2994695A1 (fr) 2014-02-28
BR112015003674A2 (pt) 2017-09-26
EA201590422A1 (ru) 2015-06-30
TWI597358B (zh) 2017-09-01
EP2888344A1 (fr) 2015-07-01
CN104603246A (zh) 2015-05-06
IN2015DN01267A (zh) 2015-07-03
FR2994695B1 (fr) 2015-10-16
WO2014029770A1 (fr) 2014-02-27
AR092373A1 (es) 2015-04-15
CN104603246B (zh) 2017-05-24
TW201425566A (zh) 2014-07-01
EA031490B1 (ru) 2019-01-31

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