Classifications

• • 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

• the 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 fuel injection systems of engines of the (bio) diesel fuel type, that is to say in particular to increase their resistance to lacquering.
• Diesel or diesel is a fuel for a diesel engine (compression engine) comprising middle distillates with a boiling point between 100 and 500 ° C.
• a diesel can be a mixture of fossil-based middle distillates and biofuels.
• biofuel we mean fuels obtained from organic matter (biomass), as opposed to fuels from fossil fuels.
• biofuels include biodiesels (also known as biodiesels) and alcohols.
• Biodiesel or biodiesel is an alternative to conventional diesel fuel.
• This biofuel is obtained from a vegetable or animal oil (including used cooking oil) transformed by a chemical process called transesterification, reacting this oil with an alcohol to obtain fatty acid esters.
• transesterification a chemical process called transesterification, reacting this oil with an alcohol to obtain fatty acid esters.
• fatty acid methyl esters (EMAG) and fatty acid ethyl esters (EEAG) are obtained respectively.
• B99 contains 99% biodiesel and 1% middle distillates of fossil origin, B20, 20% biodiesel and 80% middle distillates of fossil origin, etc.
• B0 type gasoil fuels which do not contain oxygenates are distinguished from Bx type biodiesel fuels which contain x% (v / v) of vegetable oil or fatty acid esters, most often esters. methyl esters (EMHV or EMAG).
• EMHV methyl esters
• B100 When biodiesel is used alone in engines, the term fuel is termed B100.
• Processes for preparing low-sulfur diesel or diesel fuel bases for example hydrotreatment processes in addition to reducing the sulfur content, also reduce the content of these diesel fuel gasoline bases to polycyclic aromatic compounds and in polar compounds.
• diesel or diesel fuels at low (less than 100 ppm) or very low sulfur content have a reduced ability to lubricate the engine injection system, so that for example the injection pump motor fuel can fail prematurely during the life of the engine, for example failure in high-pressure fuel injection systems, such as high-pressure rotary distributors, in-line pumps , combined pumps, with injectors.
• high-grade fuel of diesel or biodiesel type is understood to mean any diesel fuel or biodiesel fuel supplemented with at least 50 ppm by weight of reducing additives (s) and / or detergents and / or dispersants (s). ).
• FIG. 1 is a photograph of a high pressure direct injection diesel engine injector
• FIG. 2 is a photograph of a needle of a diesel engine injector with direct injection, fouled by soap and / or lacquering deposit (lacquering)
• FIG. 3 is a photograph of a nozzle of a diesel engine injector with indirect injection, fouled by coking type deposit (in English "coking")
• FIG. 4 is a photograph of a needle of a direct injection diesel engine injector, fouled by soap and / or varnish deposition (in English "lacquering")
• the lacquering phenomenon does not concern deposits which are present outside the injection system 5 or 5 '(FIGS. 1 and 3) and which are related to coking ("coking" in English) at the origin of fouling and partial or total blockage of the injection nozzles 4 or 4 '("nozzle coking" or "fouling" in English).
• Coking is a phenomenon that appears only downstream of a Diesel injection system.
• the deposits 5 'formed are characterized in that they consist of pyrolysis of the hydrocarbons entering the combustion chamber and have the appearance of carbonaceous deposits.
• the tendency to coking is much less marked. This coking is conventionally simulated by the standard engine test CEC F098-08 DW10B, especially when the test fuel is contaminated with metallic zinc.
• Lacquering is a phenomenon that occurs only in direct injection diesel engines and occurs only upstream of the i.e combustion chamber in the injection system.
• injectors 3 of direct injection diesel engines comprise a needle 2 whose lifting makes it possible to precisely control the quantity of fuel injected at high pressure directly into the combustion chamber.
• Lacquering induces the appearance of deposits 1 which appear specifically at the level of the needles 2 of the injectors 3 ( Figures 1 and 2).
• the lacquering phenomenon is related to the formation of soap and / or varnish in the internal parts of the engine injection systems for (bio) diesel fuels.
• Lacquering deposit 1 can be located on the end 4 of the needles 2 of injectors 3, both on the head and on the body of the needles 2 of the fuel injection system but also throughout the control system of the Needle lift (valves not shown) of the injection system. This phenomenon is particularly noticeable for engines using high quality (bio) diesel fuels. When these deposits are present in large quantities, the mobility of the needle 2 of the injector 3 fouled by these deposits 1 is compromised. This lacquering phenomenon can eventually generate a loss of injected fuel flow and thus a loss of engine power.
• lacquering can also cause increased engine noise and sometimes startup problems. Indeed, the parts of the needles 2 fouled by the deposits of soap and / or varnish 1 may stick to the inner walls of the injector 3. The needles 2 are then blocked and the fuel no longer passes.
• lacquering deposits There are usually two types of lacquering deposits:
• Transesterification catalysts for vegetable oils for the production of (m) ethyl esters of fatty acid esters such as sodium methanoate;
• sodium can also come from corrosion inhibitors used to transport petroleum products in some pipes, such as sodium nitrite;
• Possible sources of acids in type Bx fuels can be multiple, for example:
• o corrosion inhibitors used for the transport of petroleum products in certain pipes such as DDSA (dodecenylsuccinic anhydride) or HDSA (hexadecenylsuccinic anhydride) or some of their functional derivatives such as acids.
• DDSA dodecenylsuccinic anhydride
• HDSA hexadecenylsuccinic anhydride
• these salts are insoluble in diesel fuels with low sulfur content, and as they exist in the form of fine particles, they pass through the diesel fuel filters and are deposited inside the injectors.
• this publication the development of a motor test is described and reproduces the deposits. The publication emphasizes that only diacids generate deposits, unlike the mono carboxylic acids or the neutral esters of organic acids.
• partial esters of polyols are known per se; they may for example be prepared by esterification of fatty acid (s) and linear and / or branched polyols optionally comprising (hetero) rings of 5 to 6 atoms supporting hydroxyl functions.
• the product (s) resulting from this esterification reaction comprises a distribution in ester units, hydroxyl 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 tetraesters as well as small amounts of unreacted fatty acid (s) and polyols.
• 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, supporting functions. hydroxyls.
• the polyols will be chosen from linear polyols comprising more than three hydroxyl functions and polyols comprising at least one (hetero) ring of 5 or 6 atoms, preferably heterocycles of 4 to 5 carbon atoms. and an oxygen atom, possibly substituted by hydroxyl groups, these polyols can be taken alone or in mixture.
• the linear or branched hydrocarbon-chain polyols comprise at least four units represented in formula (I) below:
• the linear or branched hydrocarbon-chain polyols comprise at least four units represented in formula (I I) below:
• R1 and R2 are identical or different and represent either the hydrogen atom or a group -CH 3 or - C 2 H 5 , a -CH 2 -OH group.
• polyols R some comprise at least one (hetero) ring of 4 or 5 carbon atoms and an oxygen atom, optionally substituted by hydroxyl groups and correspond to the general formula (I II) below:
• polyols R 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, which is optionally substituted by hydroxyl groups.
• the polyols are selected from the group consisting of erythritol, xylitol, D-arabitol, L-arabitol, ribitol, sorbitol, malitol, risomalitol, 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 sucrose, preferably sorbitan.
• the partial esters of polyols are chosen from partial esters of sorbitan, preferably sorbitan monooleate, taken alone or as a mixture.
• the fatty acids from which the esters according to the invention are derived can be chosen from fatty acids whose chain length varies from 10 to 24 carbon atoms and / or at least one diacid substituted by at least one polymer, for example from poly (iso) butene comprising from 8 to 100 carbon atoms. They are preferably chosen for the mono acids from stearic, isostearic, linolenic, oleic, linoleic, behenic, arachidonic, ricinoleic, palmitic, myristic, lauric and capric acids, and mixtures thereof and for the diacids among alkyl or alkenylsuccinic acids. , alkyl-or alkenylmaleic.
• the fatty acids can come from the trans-esterification or saponification of vegetable oils and / or animal fats.
• Preferred vegetable oils and / or animal fats will be selected according to their concentration of oleic acid. For example, see Table 6.21 in Chapter 6 of the book Fuels & Engines by J.C. Guibet and E. Faure, 2007 edition, which lists the compositions of several vegetable oils and animal fats.
• the fatty acids may also be derived from tall oil fatty acids (Tall Oil Fatty Acids) which comprise a major amount of fatty acids, typically greater than or equal to 90% by mass, as well as resin acids and unsaponifiables in a minor amount. , ie in quantities generally less than 10%.
• Preferred additives according to the invention capable of improving the lacquering resistance of high quality (bio) diesel fuels include partial esters of sorbitan.
• additives comprise at least 50% by weight of mono- and / or diester (s) of isobutylene-succinic acid and polyols according to one of the formulas I to II.
• additives comprise at least 50% by weight of mono- and / or diester (s) of monocarboxylic acids of 12 to 24 carbon atoms and polyols according to one of formulas I to III
• the invention also relates to a package of additives for (biofuel) fuels containing at least one lacquering resistance additive as defined above and at least one or more other functional additives, such as deposition / dispersant reducing agents, -oxidants, combustion improvers, corrosion inhibitors, cold-strength additives (cloud point-improving, sedimentation rate, filterability and / or cold flow), dyes, demulsifiers, metal deactivators, defoamers, cetane improvers, compatibilizers, lubricity additives, anti-wear agents and / or friction modifiers, and one or more solvents or co-solvents .
• functional additives such as deposition / dispersant reducing agents, -oxidants, combustion improvers, corrosion inhibitors, cold-strength additives (cloud point-improving, sedimentation rate, filterability and / or cold flow), dyes, demulsifiers, metal deactivators, defoamers, cetane improvers, compatibilizers,
• the use of the additives according to the invention makes it possible to improve lacquering resistance at the fuel injectors, thus limiting the formation (deposition) of soap and / or varnish in the presence of additives such as deposit reducing agents and and / or detergent and / or dispersants.
• additives such as deposit reducing agents and and / or detergent and / or dispersants.
• the use of these additives in (bio) diesel fuels reduces the rate of clogging and deterioration of the fuel intake or injection system, in particular on the injection pump.
• the (bio) diesel fuels according to the invention may comprise middle distillates with a boiling point of between 100 and 500 ° C .; their starting crystallization temperature TCC is often greater than or equal to -20 ° C, generally between -15 ° C and +10 ° C.
• These distillates are mixtures of bases which can be chosen, for example, from distillates obtained by the direct distillation of petroleum or crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or distillate hydrocracking under vacuum, distillates resulting from processes conversion type ARDS (atmospheric residue desulfurization) and / or visbreaking.
• the (bio) diesel fuels can also contain light cuts such as distillate spirits, catalytic or thermal cracking units, isomerization alkylation units, desulfurization units, steam cracking units.
• (bio) diesel fuels may contain new sources of distillates, among which may be mentioned in particular:
• alcohols such as methanol, ethanol, butanols, ethers, (MTBE,
• ETBE Certainly generally used in combination with petrol fuels, but sometimes with heavier fuels of the diesel type,
• oils and / or their esters such as the Methyl or Ethyl Esters of Vegetable Oils or of Fatty Acids (EMHV, EEHV, EMAG, EEAG);
• the (biofuel) fuels can be used alone or mixed with conventional petroleum distillates as fuel base (s); they generally comprise long paraffinic chains of 10 carbon atoms and more, preferably C u to C 3 o-
• the (biofuel) fuels have a sulfur content of less than or equal to 500 mass ppm, advantageously less than or equal to 100 ppm by weight, and capable of falling to a content of less than or equal to 50 ppm mass or even less than or equal to 10 ppm mass (this is the case of diesel fuels for current vehicles whose sulfur content according to the European standard EN 590 currently in force must be less than or equal to 10 ppm mass).
• the lacquering resistance additives that is to say the formation of soap and / or varnish in the internal parts of the fuel injection systems of the (bio) diesel fuel engines according to the invention can be incorporated into the fuels. up to a value of up to 10% by mass.
• the concentration of partial esters according to the invention in the final fuel will be between 20 and 1000 ppm by weight, and preferably between 30 and 200 ppm by weight m / m, that is to say ppm by weight relative to the total mass of the fuel additive.
• the compositions of (bio) diesel fuel of higher quality comprise at least 20 ppm by weight of at least one additive according to the invention, and optionally at least one and / or more other functional additives.
• concentration of additive according to the invention in the composition that is to say the concentration of partial esters can vary from 20 to 1000ppm by mass, and more particularly from 30 to 200ppm mass m / m.
• the lacquering resistance additives of the present invention may be used alone or in admixture with deposition and / or detergent and / or dispersant reducers, antioxidants, combustion improvers, corrosion-resistant additives (cloud point improving, sedimentation rate, filterability and / or cold flow), dyes, demulsifiers, metal deactivators, defoamers, agents improving the cetane number, and anti-wear additives, lubricity and / or friction modifiers, co-solvents, compatibilizers, etc.
• the other functional additive (s) may be chosen from:
• procetane additives for fuels of the diesel type, mention may be made of procetane additives, in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide. and alkyl peroxides, preferably di-tert-butyl peroxide; for petrol-type fuels, there may be mentioned additives improving the octane number; for fuels such as heating oil, heavy fuel oil, marine fuel, mention may be made of methylcyclopentadienyl manganese tricarbonyl (MMT);
• MMT methylcyclopentadienyl manganese tricarbonyl
• ⁇ anti-oxidant additives such as aliphatic, aromatic amines, hindered phenols, such as BHT, BHQ;
• ⁇ anti-foam additives in particular (but not limited to) chosen, for example, from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils; examples of such additives are given in EP 861 182, EP 663 000, EP 736 590;
• ⁇ detergent or dispersant additives in particular (but not limited to) selected from the group consisting of amines, succinimides, succinamides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, Mannich bases; examples of such additives are given in EP 938,535;
• ⁇ anti-corrosion additives such as ammonium salts of carboxylic acids
• ⁇ chelating agents and / or metal sequestering agents such as triazoles, disalicylidene alkylene diamines, and especially N, N 'bis (salicylidene) 1, 3-propane diamine;
• ⁇ cold-holding additives and especially cloud-point-improving additives in particular (but not limited to) selected from the group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide, and ester polymers of fumaric / maleic acids.
• additives examples include EP 71 513, EP 100 248, FR 2 528 051, FR 2 528 423, EP 1 12 195, EP 1 727 58, EP 271 385, EP 291367; anti-sedimentation additives and / or paraffin dispersants in particular (but not exclusively) selected from the group consisting of polyamine-amidated (meth) acrylic acid / alkyl (meth) acrylate copolymers, alkenylsuccinimides derived from polyamines phthalamic acid and double chain fatty amine derivatives; alkyl phenol / aldehyde resins; examples of such additives are given in EP 261,959, EP 593,331, EP 674,689, EP 327,423, EP 512,889, EP 832,172; US 2005/0223631; US 5,998,530; WO 93/14178; polyfunctional cold operability additives chosen in particular from the group consisting of olefin and alkeny
• CFI additives such as EVA and / or EVP copolymers
• ⁇ metal passivators such as triazoles, alkylated benzotriazoles
• ⁇ acid neutralizers such as cyclic alkyl amines
• markers in particular markers imposed by the regulations, for example dyes specific to each type of fuel or fuel.
• lubricant additives especially (but not exclusively) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate and mono- and polycyclic carboxylic acid derivatives; examples of such additives are given in the following documents: EP 680 506, EP 860 494, WO 98/04656, EP 915 944, FR 2 772 783, FR 2 772 784.
• the possible other additives are generally incorporated in amounts ranging from 50 to 1, 500 ppm m / m, that is to say, mass ppm based on the total weight of the additive fuel.
• additives may be incorporated into the fuels according to any known method; for example, the additive or the mixture of additives may be incorporated in the form of a concentrate comprising the additive (s) and a solvent, compatible with the (bio) diesel fuel, the additive being dispersed or dissolved in the solvent.
• concentrates generally contain from 20 to 95% by weight of solvents.
• Solvents are organic solvents which generally contain hydrocarbon solvents.
• hydrocarbon solvents 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 or mixtures thereof.
• hydrocarbons such as commercial solvent mixtures such as Solvarex 10, Solvarex LN, Solvent Naphtha, Shellsol AB, Shellsol D, Solvesso 150, Solvesso 150 ND, Solvesso 200, Exxsol, ISOPAR and optionally co-solvents or compatibilizers, such as 2-ethylhexanol, decanol, isodecanol and / or isotridecanol.
• the invention relates to the use of at least one additive composition according to the invention incorporated in a fuel of the (bio) diesel fuel type of higher quality to improve the resistance to lacquering, ie fouling on the head and / or on the body of the needles of the fuel injection system but also throughout the system of control of the lifting of needles (valves) of the system injection, especially for engines equipped with high-pressure direct injection systems fitted to the majority of vehicles complying with the Euro 3 and most recent regulations.
• the object of the present invention also relates to the use of a (bio) diesel fuel composition as described above, to limit the deposit of soap and / or varnish in the parts.
• internal engine injection systems using said composition preferably direct injection engines, in particular high pressure direct injection engines.
• the object of the present invention is also a method for limiting the deposition of soap and / or varnish in internal parts of the injection system of a motor for (diesel) fuels (Diesel engine) having a sulfur content less than or equal to 500 ppm by mass, said process comprising the combustion in said engine of a (bio) diesel fuel composition as defined above.
• the method applies to direct injection engines, in particular high pressure direct injection engines.
• the method according to the invention avoids and prevents the formation of soap deposits and / or varnish in the internal parts of the engine injection system, for a "keep-clean" action for maintaining the cleanliness of said engine.
• the method according to the present invention eliminates the deposit of soap and / or varnish in the internal parts of the engine injection system, for a curative "clean-up" action of cleaning the engine.
• the engine used is a four-cylinder, 16-valve diesel engine with high-pressure Common Rail injection, with a displacement of 1,500 cm 3 and a power of 80 hp: the fuel injection pressure regulation is carried out in the high pressure part of the pump.
• the power point at 4,000 rpm is used for a period of 40 hours; the position of the injector in the chamber is lowered by 1 mm from 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 chamber of combustion.
• the injected fuel flow rate is adjusted to obtain an exhaust temperature of 750 ° C at the start of the test.
• the injection advance has been increased by 1.5 ° crankshaft compared to the nominal setting (we go from + 12.5 ° to + 14 ° crankshaft) always in order to increase the thermal stresses experienced by the nozzle of the injector.
• the injection pressure has been increased by 10 MPa compared to the nominal pressure (that is to say from 140 MPa to 150 MPa) and the temperature is regulated. at 65 ° C at the high pressure pump inlet.
• the technology used for the injectors requires a high fuel return, which promotes fuel degradation since it can be subjected to several cycles in the pump and the high pressure chamber before being injected into the combustion chamber.
• Lot 1 2 injectors having seen 20h of high quality fuel known for its tendency to generate lacquering.
• Lot 2 2 injectors having seen 20h of high quality fuel known for its tendency to generate lacquering + 20h of product to be evaluated.
• the characteristic temperatures of the various fluids make it possible to check the validity of the tests.
• the fuel is regulated at 65 ° C at the pump inlet
• the coolant is regulated at 90 ° C at the motor output.
• the flue gas values make it possible to control the ignition timing at the beginning of the test (target value of 3FSN) and to ensure that it is repeatable from one test to another.
• the injectors are disassembled at the end of the test to visualize and dimension the deposits formed along the needles.
• the procedure for quoting the selected hands is as follows:
• the scale of the notes varies from -2.5 (case of a large deposit) to 10 (case of a new needle without any deposit).
• the final grade is a weighted average of the notes on all the rated surfaces of the needle, ie the cone portion and the body or cylinder part of the needle.
• the zone of the cylinder (following directly the conical part) represents 68% of the overall quotation of the needle and the zone of the cone represents 32% of the overall quotation of the needle; To facilitate the quotation, each of these two zones is divided into 4.

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• 2012
  • 2012-08-22 FR FR1257939A patent/FR2994695B1/fr not_active Expired - Fee Related
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  • 2013-08-20 WO PCT/EP2013/067311 patent/WO2014029770A1/fr active Application Filing
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