TW201425566A - Additives for improving the resistance to wear and lacquering of vehicle fuels of the gas oil or bio gas oil type - Google Patents

Abstract

The present invention relates to novel anti-lacquering additives for vehicle fuels of the gas oil or bio gas oil type having a sulphur content less than or equal to 500 ppm by mass. These novel additives also improve the lacquering resistance of the higher-grade vehicle fuels of gas oil or bio gas oil type having a sulphur content less than or equal to 500 ppm by mass.

Description

Anti-wear and paint resistance additives for gasoline fuels for gasoline or bio-gasoline

The subject of the present invention relates to additives which are capable of limiting the formation of soaps and/or varnishes to the internal components of an engine-jet system of biodiesel-based automotive fuels, and in particular to increase their lacquer resistance.

Gasoline or diesel is an automotive fuel for a diesel engine (compression engine) that contains a middle distillate having a boiling point between 100 and 500 °C.

Gasoline may consist of a mixture of fossil fuels and middle distillates of biofuels.

Biomass fuel refers to automotive fuels from organic matter (biomass) compared to automotive fuels from petrochemical resources. Known biomass fuels such as biomass gasoline (or also known as biodiesel) and alcohol.

Biodiesel or biogas is an alternative to diesel engines in addition to standard automotive fuels. Biomass fuels are converted from vegetable or animal oils (including edible oils) which are chemically transesterified to react oil with alcohol to obtain fatty acid esters. Use methanol and ethanol to obtain fatty acid methyl esters (FAMEs) and fats, respectively Ethyl acetate (FAEEs).

The mixture of middle distillate and biomass gasoline derived from fossil fuel is expressed by the letter "B" followed by a number indicating the proportion of biogas present in the gasoline. Thus, B99 contains 99% biogas and 1% middle distillate derived from fossil fuels, while B20 contains 20% biogas and 80% middle distillate derived from fossil fuels.

B0 type gasoline fuel, excluding oxygenated compounds, and therefore Bx-type biogas gasoline fuel zone containing x% (v/v) vegetable oil ester or fatty acid ester, mostly methyl ester (FAME or VOME) Separate. When the raw gasoline is used alone in the engine, the above-mentioned automobile fuel is represented by B100.

In the remainder of the invention, biogas is used to represent a B0 or Bx type of automotive fuel for a diesel engine (compression engine).

In many countries, the sulfur content of biofuel gasoline fuels is reduced by very important environmental factors, especially to reduce SO ₂ emissions. For example, in Europe, the maximum sulfur content of road gasoline fuels is currently 10 ppm.

In addition to sulfur content, automotive fuel substrates that produce low sulfur gasoline or fuel, such as hydrogen treatment methods, also reduce polycyclic aromatic compounds and polar compounds in the automotive fuel base of gasoline of the above diesel engines. Gasoline or diesel automotive fuels having low (less than 100 ppm) or even lower sulfur content are currently known, which have lower ability to lubricate engine fuel injection systems, resulting in early failure of the engine fuel injection pump, for example, during the life of the engine. For example, high pressure automotive fuel injection systems, such as high pressure rotary distributors, in-line pumps, and combined pump-nozzle components.

In order to compensate for the loss of compounds, ensure the lubrication of automotive fuels. Various lubricants and/or anti-wear and/or friction modifying additives are known to be added to commercially available fuels. The above characteristics have been extensively discussed in the patents EP 915 944, EP 839 174 and EP 680 506.

Commercially available diesel must comply with national or supranational specifications (eg EN590 for diesel sold in Europe). For commercial fuels, additives for use (chemicals added to fuels to improve their properties, such as detergents, friction-reducing additives, anti-corrosion agents, anti-foaming agents, and additives to improve cold resistance) There is no legal regulation; oil companies and distributors can add or not add additives to the fuel from the oil. From a commercial point of view, in the field of fuel sales, "standard or entry" fuels with little or no added additives, and advanced fuels with one or more additives to improve their performance (effective in regulations) There is a difference.

By advanced fuel diesel or biodiesel as referred to in the context of the present invention is meant the addition of at least 50 ppm by weight of a deposition reducing agent and/or detergent and/or dispersant additive.

1‧‧‧deposition

2‧‧‧Injection needle

3‧‧‧Injector

4‧‧‧ nozzle

5‧‧‧Injection system

Figure 1 is a photograph of a diesel engine injector equipped with high pressure direct injection.

Figure 2 is a photograph of the spray (painting) type of the spray needle of the direct injection diesel engine with soap and/or varnish type.

Figure 3 is a photograph of coking deposits on the nozzle of a direct injection diesel engine.

Figure 4 is a photograph of the spray (painting) type of the spray needle of the direct injection diesel engine with soap and/or varnish type.

As shown in Figures 1 and 2, when using advanced biomass gasoline vehicle fuel, deposition 1 occurs on the injection needle 2 of the injector 3 in the diesel engine injection system, particularly of the Euro 3 or Euro 6 type. Thus, additives deposited using antiwear and/or friction modifiers and/or anti-coking types sometimes have a paint resistance effect that is less than satisfactory or even very unsatisfactory. The formation of deposition 1 is commonly referred to as "painting" and will be followed by the term or abbreviation IDID (internal diesel nozzle deposition).

Within the meaning of the present invention, the lacquering phenomenon is not related to the deposition existing outside the injection system 5 or 5' (Figs. 1 and 3), which is related to coking, thereby increasing fouling and nozzles 4 or 4' Part or overall blockage (nozzle coking or fouling).

Lacquering and coking are two different phenomena, the differences being: - the cause of the formation of the deposit, - the appearance of the deposit, - the location of the deposit.

Coking is only formed downstream of the diesel injection system.

As shown in Fig. 3, the formed deposit 5' is formed by pyrolysis of hydrocarbons into the combustion chamber, which has the appearance of carbonaceous deposits. In high-pressure direct injection diesel engines, there is less tendency to coke. Coking is tested with the CEC F098-08 DW10B standard engine test, especially when the automotive fuel tested contains metallic zinc.

The automotive fuel injection of the indirect injection engine is not directly carried out in the combustion chamber as a direct injection engine. The example described in US 4,604,102 has a prechamber in front of the combustion chamber where the fuel is injected. The pressure and temperature of the pre-chamber are lower than the combustion chamber of the direct injection engine.

In this case, the carbonaceous particles generated by pyrolysis of the automobile fuel are deposited on the surface of the nozzle 4' of the syringe (throttled diesel nozzle) to block the small hole 6 of the nozzle 4' (Fig. 3). Only the surface of the nozzle 4' exposed to the combustion gases presents a risk of carbon deposition (coking). In terms of performance, coking results in a reduction in engine power.

The lacquering phenomenon occurs only in direct injection diesel engines and only occurs upstream of the combustion chamber, ie the injection system.

As shown in Fig. 1 and Fig. 2, the injector 3 of the direct injection diesel engine is provided with an injection needle 2 whose rise can accurately control the amount of diesel fuel directly injected into the combustion chamber at a high pressure.

The deposition 1 caused by the lacquer is particularly present in the injection needle 2 of the ejector 3 (Fig. 1 and Fig. 2). The lacquering phenomenon is related to the soap and/or varnish formed on the internal components of the engine injection system of the biodiesel diesel. The paint deposit 1 can be located at the tail 4 of the injection needle 2 of the injector 3, in the head and tail of the injection needle 2 in the vehicle fuel injection system, but also in the entire injection needle of the injection system to improve the control system (pump not shown ). The above phenomenon occurs particularly in automobile engines that use advanced biomass gasoline. When the amount of deposition is large, the mobility of the injection needle 2 of the ejector 3 is damaged by the deposition 1. The above-mentioned lacquering phenomenon will eventually result in a decrease in the fuel flow rate of the injected vehicle, thus losing engine power.

In addition, unlike coking, lacquering tends to cause an increase in engine noise and sometimes difficulty in starting. A portion of the spray needle 2 on which the soap and/or varnish 1 is deposited is attached to the inner side wall of the ejector 3. The injection needle 2 is blocked so that the fuel can no longer pass.

There are usually two types of lacquer-deposited deposits: 1. A white powder-like deposit that has been analyzed to contain Sodium (such as sodium carboxylate) and / or calcium (first deposition); 2. Organic deposition, such as colored paint concentrated on the spray needle body (second deposition).

For the first type of deposition, Bx-type fuels for biodiesel motor fuels have many possible sources of sodium: • Catalysts for transesterification of vegetable oils, which are used to make esters of fatty acid (ethyl) ethyl esters, such as sodium formate. • Another possible source of sodium is the corrosion inhibitor for the pipeline used to transport petroleum products, such as sodium nitrate; • Finally, accidental exogenous contamination, such as from water or air, may also bring sodium into the fuel (sodium It is a very common material component).

There are many possible sources of acid in Bx fuels, such as: • Residual acids in biodiesel (refer to the maximum allowable acid content specified in EN 14214); • Corrosion inhibitors for transporting petroleum products to specific pipelines, such as dodecene A succinic anhydride (DDSA) or a hexadecenyl succinic anhydride (HDSA) or a functional derivative of the foregoing (eg, an acid).

Regarding the above second organic deposition, some publications mention that it may be a deposition reducer/dispersant (for example, a PIBSI type cleaner, which is a derivative of a polyamine) and an acid (other than other substances in the raw gasoline). Produced by the reaction of impurities contained in the ester of a fatty acid.

Authors M Ziejewski and HJ Goettler describe the lacquer phenomenon in the publication SAE 880493, "The lacquer deposits produced by sunflower oil lead to reduced mobility of the spray needle" and its operation for engines operating with sunflower oil as fuel Harmful consequences.

Authors J. Ullmann, M Geduldig, H Stutzenberger (Robert Bosch GmbH), and R Caprotti, G Balfour (Infineum) in the publication SAE 2008-01-0926 "Investigating the Formation and Prevention of Internal Diesel Jet Deposition", also describing acid and deposition Reducer/dispersant reaction to explain the second deposition.

In addition, the authors S. Schwab, J. Bennett, S. Dell, J. Galante-Fox, A. Kulinowsky and Keith T. Miller in the publication SAE International, 2010-01-2242, "Internal spray deposition of high-pressure general train diesel engines It is stated that the internal parts of the jet are usually covered with a light-colored deposit visible to the naked eye. The above analysis shows that it mainly contains the sodium salt of alkenyl (hexadecenyl or dodecenyl) succinic anhydride; sodium is derived from a dehydrating agent, a caustic solution for refining, water at the bottom of the reaction tank, seawater, It is used as a succinic anhydride to prevent corrosion agents, or as a multifunctional additive. Once formed, these salts are insoluble in low sulfur diesel fuels, and they are fine particles that can be deposited inside the injection system through the diesel fuel filter. In this publication, mentioning the development of engine testing, it is possible to re-deposit. This publication emphasizes that only diacids are deposited compared to neutral esters of mono or organic acids.

Authors R. Caprotti, N. Bhatti and G. Balfour in the publication SAE International 2010-01-2250, "Deposition Control of Modern Diesel Fuel Injection Systems", investigate the internal deposition of the same injection system and confirm the presence of sediment It is related to a specific fuel (B0 or contains FAME (Bx)), and is not equipped with a specific vehicle (light vehicle or heavy vehicle) equipped with modern motorization (common rail). The above authors found new deposition reducer/dispersant properties for various deposits (focusing) And paint) are effective.

The present invention proposes a preventive and effective additive which limits the deposition of soap and/or varnish on the internal components of the spray system, i.e., improves the paint resistance of automotive engines using advanced biomass gasoline and/or biodiesel type, such additives Containing a sulfur content of less than or equal to 500 ppm by mass, which contains at least 50 ppm by mass of a deposition reducing agent and/or detergent and/or dispersant. The above additives can thus prevent the formation (prevention) of deposition, and can perform removal of the deposition (effective treatment) with a jet cleaner when deposition is formed.

The problem of paint resistance of automotive gasoline fuels can be achieved by using at least one additive containing at least 50% by mass of a portion of a polyol ester containing an x ester unit, a y hydroxylation unit, and a z ether unit. Wherein x is an integer from 1 to 10, y is an integer from 1 to 10, z is an integer from 0 to 6, and x is preferably an integer from 1 to 10, and y is preferably an integer from 3 to 10, z It is preferably an integer of 0 to 6.

Polyol esters are essentially derived by esterification of a fatty acid with a linear and/or branched polyol wherein the polyol selectively contains from 5 to 6 atomic (hetero) rings. The product derived from this esterification reaction includes a distribution of an ester unit, a hydroxy unit, and an ether unit, wherein x is from 1 to 4, y is from 1 to 7, and z is from 1 to 3. Typically such a synthesis will result in a mono-, di-, tri-, and selective tetra-ester with a small amount of unreacted fatty acid and polyol mixture.

According to one embodiment, the polyol ester is essentially obtained by esterification of a fatty acid with a linear and/or branched polyol, wherein the polyol selectively contains a heterocycle having 4 to 5 carbon atoms and a hydroxyl atom bearing a hydroxyl group.

Under the framework of the present invention, the polyol is selected from linear polyols containing more than 3 hydroxyl groups and polyols containing at least one 5 to 6 atomic (hetero) ring. The polyhydric alcohol is preferably a heterocyclic ring of 4 to 5 carbon atoms and a hetero atom optionally having an oxygen atom of a hydroxyl group, and the above polyhydric alcohol may be used singly or in combination.

For the discussion that follows, polyols are indicated by R in the following chemical formula.

In the polyol R, a linear or branched hydroxy chain containing at least four units represented by the following chemical formula (I): H-(OCH ₂ ) _p -(CHOH) _q -(CH ₂ OH) (I)

Where p and q are integers, p is equal to or greater than 0, q is greater than 2, and the above number does not exceed 10.

In the polyol R, a linear or branched hydroxy chain containing at least four units represented by the following chemical formula (II): H-(OCH ₂ ) _p -(CR1R2) _q -(CH ₂ OH) (II)

Wherein p and q are integers, p is equal to or greater than 0, q is greater than 1, the above number does not exceed 5, and R1 and R2 are the same or different hydrogen atoms or -CH ₃ or -C ₂ H ₅ or -CH ₂ -OH.

In the polyol R, a (hetero) ring partially containing at least one or four carbon atoms and an oxygen atom selectively substituted with a hydroxyl group correspond to the following chemical formula (III):

Where s and t are integers, when s is equal to 1, t is equal to 3, and when s is equal to 0, t is equal to 4.

The polyol R, a heterocyclic ring partially containing at least two 4 or 5 carbon atoms and an oxygen atom, is bonded between an acetal chain formed between a hydroxyl group and each ring, wherein the heterocyclic ring is selectively substituted with a hydroxyl group.

Polyols are free erythritol, xylitol, arabitol, nucleus Sugar alcohol, sorbitol, maltitol, isomalt, lactitol, sorbitan, heptaerythritol, mannitol, pentaerythritol, 2-hydromethyl-1,3-propanediol, 1,1 A group consisting of 1-tris(hydroxymethyl)ethane, trimethylolpropane, and a carbohydrate such as sucrose, fructose, maltose, glucose, and sucrose, preferably sorbitan.

According to a preferred variant, part of the polyol ester is selected from the group consisting of sorbitanol, preferably sorbitan monooleate, alone or in combination.

The fatty acids derived from the esters according to the invention are selected from fatty acids having a chain length of from 10 to 24 carbon atoms and/or at least one diacid substituted with at least one polymer, for example poly(iso) having from 8 to 100 carbon atoms. Butene. Preferably, the above is selected from the group consisting of stearic acid, isostearic acid, linolenic acid, oleic acid, linoleic acid, behenic acid, arachidonic acid, ricinoleic acid, palmitic acid, myristic acid, lauric acid, strontium Acidic monoacids, as well as mixtures of the above and/or diacids selected from alkane- or alkenyl succinic acid, alkane- or alkenyl maleic acid.

Fatty acids may be derived from the esterification or saponification of vegetable oils and/or animal fats. Preferred vegetable oils and/or animal fats are selected based on their oleic acid concentration. Reference is made to J.C. Guibet and E. Faure, Carburants & Moteurs, Chapter 6, Table 6.21, published in 2007, which provides examples of several plant oils and animal fats.

Fatty acids can also be derived from tall oil, which mostly contains fatty acids, typically greater than or equal to 90% of the resin acid, and a few unsaponifiables, that is, less than 10%.

According to the present invention, it is possible to improve the fuel of advanced biomass diesel fuel The lacquer-resistant additive contains a portion of sorbitan ester.

Other preferred additives are mono- and/or diesters containing at least 50% isobutyl succinic acid and the polyols of formulas I to III according to the invention.

Other preferred additives comprise at least 50% of a monocarboxylic acid of from 12 to 24 carbon atoms, and a mono- and/or diester of a polyol of formulas I to III of the present invention.

The invention also relates to an additive for a biofuel gasoline vehicle fuel comprising at least one lacquer resist additive as previously defined, and at least one or more other functional additives, such as a deposition reducer/dispersant, an antioxidant, a combustion Improver, rust inhibitor, low temperature resistant additive (improved cloud point, precipitation rate, filterability and/or low temperature fluidity), colorant, deemulsifier, metal passivator, anti-foaming agent, modified cetane number Reagents, cosolvents, compatibilizers, other lubricants, antiwear agents and/or friction modifiers, and optionally one or more solvents.

The use of the additive of the present invention can improve the paint resistance of the fuel injector in the presence of a deposition reducing agent and/or a cleaning agent and/or a dispersing agent, thereby limiting the deposition of soap and/or varnish. The use of the above additives in biofuel gasoline fuels can reduce fuel entry or injection systems, particularly syringe pumps.

Biodiesel motor fuel (liquid fuel for compression engines) can contain middle distillates with a boiling point between 100 and 500 ° C; the initial crystallization point ICT is usually higher than or equal to 20 ° C, usually -15 and +10 ° C between. Distillate is a mixture of substrates selected from, for example, direct distillation of crude oil hydrocarbons or gasoline, vacuum fractions, hydrotreated fractions, fractions derived from cavitation and/or hydrocracking vacuum distillation, ARDS processes (often Obtained by fractionation of pressure distillation desulfurization and/or visbreaking and mild cracking.

Diesel fuels may also contain light cuts such as gasoline from distillation, catalyst or thermal cracking, alkylation, isomerization, desulfurization, steam cracking.

In addition, diesel fuels may contain novel sources of fractions, such as: - heavier fractions from cracking and visbreaking processes, concentrated in heavy paraffins, which contain more than 18 carbon atoms; - from eg Fisher-Trop Syngas-converted synthetic fractions; - synthetic fractions of biomass from plant and/or animal sources, such as NexBTL, alone or in mixtures; - Coker gas oil; - alcohols, for example Methanol, ethanol, butanol, ether, (MTBE, ETBE, etc.), usually used in mixtures with gasoline fuels, but sometimes heavier fuels of gas oils; - and / or animal oils and / or their esters, for example A methyl or ethyl ester of vegetable oil or fatty acid (VOME, FAME, VOEE, FAEE); - a plant and/or animal oil hydrotreated and/or hydrocracked and/or hydrodeoxygenated (HDO).

The novel fuel and heated fuel bases described above may be used alone or as a fuel base in combination with conventional gasoline mid-range fractions; typically, they comprise a long paraffin chain of greater than or equal to 10 carbon atoms, preferably _C14 to _C30 .

Under the framework of the invention, a diesel fuel having a sulfur content of less than or equal to 500 ppm is advantageously less than or equal to 100 ppm mass and can be reduced to less than or equal to 50 ppm mass, or even less than or equal to 10 ppm mass ( That is, below or equal to the current EN590 standard according to EU regulations. 10ppm mass).

Providing an additive for lacquer resistance, that is, an additive for reducing soap and/or varnish formed in an internal component of an injection system in a biofuel gasoline fuel according to the present invention, may be added to the fuel in an amount of up to 10% by mass . The concentration of the partial ester in the final automotive fuel according to the present invention is from 20 to 1000 ppm by mass, preferably from 30 to 200 ppm by mass, i.e., the total mass ppm relative to the fuel to which the additive is added.

According to an embodiment, the advanced biomass gas oil fuel composition comprises at least 20 ppm by mass of at least one additive according to the invention, and comprises at least one or more other functional additives, that is to say a partial ester concentration of from 20 to 1000 ppm and in particular 30 to 200 ppm mass m/m.

In addition to other functional additives, the paint resist additive of the present invention may be used alone or in combination, such as a deposition reducer/dispersant, an antioxidant, a combustion improver, a corrosion inhibitor, a low temperature resistant additive (a modified cloud point, Precipitation rate, filterability and/or low temperature fluidity), colorants, demulsifiers, metal passivators, anti-foaming agents, cetane-modified agents, anti-wear agents, lubricity additives and/or friction modifiers , cosolvents, compatibilizers, etc.

Other functional additives may be not limited, selected from: ◆ improved combustion agent; automotive fuels of the gas oil type, mention may be made of cetane number enhancing additives, especially (but not limited to, selected from alkyl nitrates, preferably 2 -ethylhexyl nitrate, aryl hydroperoxide, preferably benzyl hydroperoxide, and alkyl hydroperoxide, preferably dibutyl butyl peroxide; for gas oils, there are ten Hexane value improver; for domestic fuel oil, heavy fuel oil, naval diesel, there will be methylcyclopentadienyl manganese tricarbonyl (MMT); ◆Antioxidant additives, such as aliphatic, aromatic amines, hindered phenols, such as BHT, BHQ; ◆ deemulsifiers or demulsifiers; ◆ antistatic or conductive improvers; ◆ colorants; ◆ anti-foaming agents, special (but Not limited to) selected from plant or animal oil-derived polydecane, oxyalkylated polydecane, and fatty acid decylamine; EP 861 182, EP 663 000, EP 736 590 have examples of providing the above additives; ◆ detergents or dispersing additives, especially (but not limited to) a free amine, amber imine, succinimide, alkenyl amber imine, polyalkylamine, polyalkylamine, polyetheramine, Mannich; a vane of the above additives such as EP 938 535; ◆ corrosion inhibitors, such as amine salts of carboxylic acids; ◆ binders and / or metal sequestrants, such as triazoles, di-salicylidene alkylene diamines, and especially N, N'-bis (Asia Salicyl) propane diamine; ◆ anti-low temperature additive and especially additives for improving cloud point, but not limited to, including long chain olefin / (meth) acrylate / maleimine polycondensation And a group of polymers that go to maleic acid/maleate. Examples of such additives are disclosed in EP71513, EP100248, FR2528051, FR2528423, EP112195, EP172758, EP271385, EP291367; anti-precipitation and/or dispersant additives, in particular for paraffin waxes (but not limited to), are freely aminated by polyamines ( Methyl)acrylic acid/alkyl (meth) acrylate copolymer, polyamine alkylene succinate, palmitic acid, and double chain fatty amine derivatives; group of alkyl phenol/aldehyde resins; examples of the above additives Published in EP261519, EP593331, EP674689, EP327423, EP512889, EP832172, US2005/0223631, US5998530, WO93/14178; multifunctional low temperature operating additives, especially groups selected from the group consisting of free olefin- and alkene nitrate base polymers, as disclosed in EP 573 490; ◆ other additives for improved low temperature resistance and filterability (CFI) , for example, EVA and / or EVP copolymer; ◆ metal passivators, such as triazoles, alkylated benzotriazoles; ◆ neutralizers, such as cycloalkylamines; ◆ labeling agents, especially regulatory requirements, such as a specific coloring agent for each fuel or heating fuel oil; a fragrance or a neutralizing odor agent, such as disclosed in EP 1 159 514; a lubricating additive, an anti-wear agent and/or a friction modifier other than the above; In particular, without limitation, the selection of free fatty acids and their esters or derivatives, in particular glycerol monooleate and mono-polycyclic carboxylic acid derivatives; examples of such additives are disclosed in the following documents: EP 680506, EP 860494, WO 98/04656, EP 915 944, A group consisting of FR2772783 and FR2772784.

Other optional additives are typically added in an amount of from 50 to 1500 ppm m/m, that is, relative to the overall quality of the automotive fuel containing the additive.

The above additives may be added to the fuel by any means, for example, a concentrated additive-containing solvent and a solvent compatible with the biodiesel fuel may be added, and the additive may be dispersed or dissolved in the solvent. The above concentrates usually contain from 20% to 95% by mass of solvent.

Those skilled in the art can readily vary the concentration of the additive according to the present invention and dilute any of the additives in a solvent. Other components that may be present are esterification reactions and/or other functional additives added to the final automotive fuel.

The above solvent is an organic solvent and usually contains a carbonyl solvent. Solvent Examples include petroleum fractions such as naphtha, kerosene, fuel oil; aliphatic and/or aromatic aryl carbonyls such as hexane, pentane, decane, pentadecane, toluene, xylene and/or Or ethylbenzene and alkoxyalkanols, such as 2-butoxyethanol and/or carbonyl mixtures, such as commercially available solvents such as Solvarex 10, Solvarex LN, naphtha, Shellsol AB, Shellsol D, Solvesso 150, Solvesso 150ND, Solvesso 200 Exxsol, ISOPAR and optional co-solvents or compatibilizing agents such as 2-ethylhexanol, decyl alcohol, isodecyl alcohol and/or isodecyl alcohol.

The present invention relates to the use of at least one additive composition according to the present invention for the use of advanced biomass gasoline for improving paint resistance, that is, a spray needle body located at the head of a fuel injection system nozzle and/or an injection system, and an overall nozzle suspension Dirt on the body of the control system (pump), especially for engines that provide high-pressure direct fuel injection systems, most of which comply with Euro3 and newer regulations.

According to an embodiment, the object of the present invention is to use a composition as described above in a biodiesel automotive fuel to limit the deposition of soap and/or varnish in the internal components of the injection system using the above composition, more preferably direct injection The engine, especially the high pressure direct injection engine.

The object of the present invention is also directed to a method of limiting the deposition of soap and/or varnish in an internal component of an injection system in a biomass gasoline automobile fuel (diesel engine) having a sulfur content of less than or equal to 500 ppm by mass, the method comprising The above-described biodiesel automobile fuel composition is burned in the above engine. The above method is preferably used for a direct injection engine, particularly a high pressure direct injection engine.

Thus, the method according to the invention avoids and prevents the deposition of soap and/or varnish on the internal components of the spray system while keeping the engine clean. An advantage of the method according to the invention is that the soap and/or varnish is deposited in the internal elements of the injection system Piece, clean the engine in a therapeutic manner.

[Examples]

The inventors have also developed novel, reliable and robust methods for assessing the sensitivity of biomass gas oil fuels, particularly the lacquer resistance of advanced fuels. The above method, compared to the method disclosed in the aforementioned documents, is not a laboratory method, but is of interest to the industry based on engine testing and is capable of quantifying the effectiveness of additives or additive compositions for paint resistance. The method for measuring paint resistance developed by the above inventors is detailed as follows:

The engine used is a four-cylinder, 16-valve, high-pressure injection common rail fuel engine with a cylinder displacement of 1500 cm ³ and 80 horsepower: the fuel injection pressure is regulated at the high pressure portion of the pump.

The power point of the ̇ is 4000 rpm at 40 h, and the position of the ejector in the combustion chamber is 1 mm lower than the normal position, on the one hand, the heat energy release of the combustion is increased, and on the other hand, the ejector is closer to the combustion chamber.

̇ Adjust the flow rate of the fuel injection so that the temperature of the exhaust gas is 750 ° C at the start of the test.

̇ Relative to the general setting (crankshaft changed from +12.5° to +14°), the injection system propelled by 1.5° crankshaft, still attempting to increase the thermal stress applied to the nozzle.

Finally, to increase the thermal stress on the fuel, the injection pressure is increased by 10 MPa with respect to the normal pressure (that is, from 140 MPa to 150 MPa), and the inlet temperature of the high pressure pump is set at 65 °C.

The technology used in the ejector requires a high fuel return, which can improve fuel degradation because the fuel is subjected to several cycles in the high pressure pump and common rail in the combustion chamber before being injected.

A variation of the above method involves testing the cleaning effect (ie, cleaning type 1 and/or type 2 deposition). It is based on the aforementioned method, but is divided into two 20-hour phases:

● The first 20 hours is the use of advanced gas oil B7 (containing PIBSI type cleaner and ACID friction modifier), which is easy to cause lacquering. After 20 hours, two of the four engines were disassembled for evaluation to confirm the amount of deposition present and replace the two new engines.

● Use the pre-evaluated product for 20 hours after the test. At the end of the test (40 hours total), the injector was disassembled for evaluation.

At the end of the test, there are three groups of two engines: ● Group 1: two injectors experiencing 20 hours of advanced fuel that is prone to paint resistance; ● Group 2: two hours of advanced fuel operation that is prone to paint resistance Ejector + 20 hours pre-evaluated product; ● Group 3: Two injectors undergoing pre-evaluation for 20 hours Results: To ensure correctness of the results, various parameters are monitored during the test: power, torque and fuel Consumption, which may indicate whether the ejector is fouled or the operation has deteriorated due to the formation of deposits since the entire test operating point is the same.

The characteristic temperatures of the various liquids (coolant, fuel, oil) allow the correct performance of the test to be monitored. The fuel was adjusted to 65 ° C at the pump inlet and the coolant was adjusted to 90 ° C at the engine outlet.

The smoke value allows the burn time to be monitored at the start of the test (target value 3FSN) and to ensure that it repeats the test properly.

The spray system was removed after testing to inspect and evaluate the deposit formed along the spray needle. The procedure used to score jets is as follows: the fraction scales from -2.5 (thick deposition) to 10 (new jets without any deposit). The final score is the overall evaluation of the nozzle surface as a weight, that is, the conical portion of the injection needle and the body or cylindrical portion.

Thus the cylindrical region (followed by the conical portion) represents an evaluation of the 68% integral needle, and the conical area is 32% of the overall injection needle evaluation; for ease of evaluation, the two regions are divided into four. The percentage shown in Fig. 4 is 1/4 of the area of the injection needle, and the overall surface area is thus 17x4 = 68%.

The threshold for performance is set for this rating procedure: result <4=poor; result>4=satisfactory.

The following examples are intended to illustrate the invention without limiting the invention.

Example 1 - Measuring Paint Resistance

Based on the above procedure for measuring paint resistance, several additive groups were evaluated for addition to the gas oil combination representing the French market (B7 = French-made gas oil containing 7% FAME (fatty acid methyl ester) and in accordance with EN 590). The fuel composition for each test, and the results are shown in Table 1.

The quantity shown in Table 1 is mass (m/m).

The above tests clearly show that the product of the present invention prevents and limits the effect of varnish or soap deposition (maintained clean), and the evaluation results of the spray needle are better than those of the automotive fuel containing only PIBSI which will form soap on the jet injection needle.

Example 2 - Measuring Paint Resistance

Based on the above procedure for measuring paint resistance, several additive groups were evaluated for addition to the gas oil combination representing the French market (B7 = French-made gas oil containing 7% FAME (fatty acid methyl ester) and in accordance with EN 590). The fuel composition for each test, and the results are shown in Table 2. Tests G, G', G" correspond to the same test, G corresponds to the first group of injectors, G' corresponds to the second group of injectors, and G" corresponds to the third group of injectors.

The quantity shown in Table 2 is mass (m/m).

The above test shows an effective treatment (cleaning effect) of the product of the present invention, that is, removal of soap or varnish-like deposits that have been formed on the spray needle, since the injector G' is evaluated more than the injector G (a large number of clean injection needles have been started) ) is superior, and its preventive effect (maintaining the cleaning function) is confirmed because the injector G" score is higher.

1‧‧‧deposition

2‧‧‧Injection needle

3‧‧‧Injector

4‧‧‧ nozzle

5‧‧‧Injection system

Claims (24)

An additive for use in automotive fuels for limiting the production of soap and/or varnish to internal gasoline in an engine injection system having a sulfur content of less than or equal to 500 ppm by mass, containing at least 50% by mass of a portion of the polyol An ester comprising x units, y hydroxyl groups and z ether units, wherein x is an integer from 1 to 10, y is an integer from 1 to 10, and z is an integer from 0 to 6. An additive for use in automotive fuels for limiting the deposition of soap and/or varnish into the internal components of an engine injection system as described in claim 1 wherein the polyol ester is fatty acid and linear and/or The branched polyol is esterified, wherein the polyol optionally contains 5 to 6 atomic (hetero) rings, preferably 4 to 5 carbon atoms, and a heterocyclic ring having an oxygen atom of a hydroxyl group. An additive for use in an automobile fuel for limiting the deposition of soap and/or varnish into an internal component of an engine injection system, as described in claim 1 or 2, wherein the ester unit of the polyol ester is hydroxylated. The distribution of units and ether units is x from 1 to 4, y from 1 to 7, and z from 1 to 3. An additive for use in an automobile fuel for limiting the deposition of soap and/or varnish into an internal component of an engine injection system as described in claim 1, 2 or 3, wherein the polyol R is selected from the group consisting of a linear polyol having more than 3 hydroxyl groups, and the polyol contains at least one heterocyclic ring of 5 or 6 atoms, preferably a heterocyclic ring of 4 to 5 carbon atoms and 1 oxygen atom, which may be optionally substituted with a hydroxyl group, the above polyol It can be used singly or in a mixture. An additive for automotive fuel use of raw gasoline for limiting the deposition of soap and/or varnish in internal components of an engine injection system, as claimed in claim 1, 2, 3 or 4, wherein R has at least 4 a polyol of the following formula (I): H-(OCH ₂ ) _p -(CHOH) _q -(CH ₂ OH) (I) wherein p and q are integers, p is equal to or greater than 0, and q is greater than 2, And the above figures do not exceed 10. An additive for automotive fuel use of raw gasoline for limiting the deposition of soap and/or varnish in internal components of an engine injection system, as claimed in claim 1, 2, 3 or 4, wherein R has at least 4 The unit polyol of the following formula (II): H-(OCH ₂ ) _p -(CR1R2) _q -(CH ₂ OH) (II) wherein p and q are integers, p is equal to or greater than 0, and q is greater than 1, And the above number does not exceed 5, and R1 and R2 are the same or different hydrogen atoms or -CH ₃ or -C ₂ H ₅ or -CH ₂ OH. An additive for use in automotive fuels for limiting the production of soap and/or varnish to internal fuels of internal components in an engine injection system, as claimed in claim 1, 2, 3 or 4, wherein R has at least 2 A heterocyclic ring of 4 to 5 carbon atoms and 1 oxygen atom, which is linked by an acetal chain formed between hydroxyl groups in each ring, and the above heterogeneous selectivity may be substituted with a hydroxyl group. An additive for use in automotive fuels for limiting the production of soap and/or varnish to the internal components of an engine injection system as described in claim 1, 2, 3 or 4, wherein a portion of the polyol ester is It is selected from the group of sorbitan esters, preferably sorbitol oleate, either alone or in a mixture. The use of the internal components of the engine spray system to limit the deposition of soap and/or varnish as described in claim 1, 2, 3, 4, 5, 6, 7, or 8. An additive for automotive fuels of gasoline, wherein the polyol R is selected from the group consisting of erythritol, xylitol, arabitol, ribitol, sorbitol, maltitol, isomalt, lactitol, sorbitan , heptaerythritol, mannitol, pentaerythritol, 2-hydromethyl-1,3-propanediol, 1,1,1-tris(hydroxymethyl)ethane, trimethylolpropane, and carbohydrates such as sucrose, A group of fructose, maltose, glucose, and sucrose is preferably sorbitan. Automotive fuel use as described in claim 1, 2, 3, 4, 5, 6, 7, 8 or 9 to limit the production of soap and/or varnish to the internal components of the engine injection system An additive, wherein a part of the polyol ester is obtained by reacting a polyol with at least one fatty acid having a chain length of 10 to 24 carbon atoms and/or at least one diacid substituted with at least one polymer, for example, containing 8 to 100 carbons. Atomic poly(iso)butene. An additive for use in automotive fuels for limiting the deposition of soap and/or varnish into the internal components of an engine injection system as described in claim 10, wherein a portion of the polyol ester is a free monoester or diester. a group consisting of stearic acid, isostearic acid, linolenic acid, oleic acid, linoleic acid, behenic acid, arachidonic acid, ricinoleic acid, palmitic acid, nutmeg Acid, lauric acid, monoacid of citric acid, and mixtures of the above and/or diacids selected from alkane- or alkenyl succinic acid, alkane- or alkenyl maleic acid. An automobile fuel that uses an additive as described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 for biogas to limit soap and/or varnish deposition on the engine An internal component in the injection system wherein the additive has a sulfur content of less than or equal to 500 ppm mass. The use of additives in the production of gasoline as described in claim 12 The vehicle fuel is used to limit the deposition of soap and/or varnish to the internal components of the engine injection system, wherein the additive is added to the automotive fuel of the engine, preferably at a concentration of at least 20 ppm by mass. The automotive fuel using the additive in biogas gasoline as described in claim 12 or 13 is used to limit the deposition of soap and/or varnish to internal components in an engine injection system, wherein the engine is a direct injection engine. An automotive fuel for biomass gasoline having a sulfur content of less than or equal to 500 ppm by mass and comprising at least one of the claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 An additive according to the invention, and optionally containing at least one or more other functional additives, such as deposition reducing agents and/or detergents and/or dispersants, antioxidants, combustion improvers, corrosion inhibitors, anti-low temperature additives, coloring Agents, demulsifiers, metal passivators, anti-foaming agents, cetane-modified agents, lubricants, anti-wear agents and/or friction modifiers, as well as co-solvents and compatibilizers. The automotive fuel of the raw gasoline according to claim 15 of the patent application, which contains one or more of up to 10% by mass, as in the scope of claims 1, 2, 3, 4, 5, 6, 7, 8, and 9. Additives as described in 10 or 11. An automotive fuel for biomass gasoline having a deposition reducer/cleaner/dispersant of at least 50 ppm by mass and comprising at least 20 ppm of mass as claimed in claims 1, 2, 3, 4, 5, 6, 7, 8 An additive according to clause 9, 10 or 11 and optionally comprising at least one or more other functional additives, such as a deposition reducing agent and/or a cleaning agent and/or a dispersing agent, an antioxidant, a combustion improver, a corrosion inhibitor , low temperature resistant additives, colorants, demulsifiers, metal passivators, anti-foaming agents, cetane-modified reagents, lubrication Agents, antiwear agents and/or friction modifiers, as well as cosolvents and compatibilizers. The automotive fuel of the raw gasoline according to claim 15, claim 16, wherein the single- and di-ester concentrations are 20 to 1000 ppm by mass, preferably 30 to 200 ppm by mass/m. An automotive fuel that uses an additive as described in claim 15, claim 16, 17 or 18 for biogas to limit the deposition of soap and/or varnish to internal components in an engine injection system. The automotive fuel using the additive in biogas gasoline as described in claim 19 is used to limit the deposition of soap and/or varnish to internal components in an engine injection system, wherein the engine is a direct injection engine. A method of limiting the deposition of soap and/or varnish to internal components in an engine injection system of automotive fuel using biomass gasoline having a sulfur content of less than or equal to 500 ppm by mass, the method comprising use as in claim 15 The composition of item 16, 17, or 18 is combusted by the engine. A method of limiting the soap and/or varnish deposited in an internal component of an engine injection system using automotive fuel for biofuels as described in claim 21, wherein the engine is a direct injection engine. A method of limiting the soap and/or varnish deposited in an internal combustion engine of an automotive fuel injection system using biofuels as described in claim 21 or 22, wherein the avoidance and prevention of soap and/or varnish deposition is limited. In order to keep the engine clean. A method of limiting the soap and/or varnish deposited on an internal component of an engine injection system of a vehicle fuel using biodiesel as disclosed in claim 21, 22 or 23, wherein the internal components deposited in the engine injection system are removed of Soap and / or varnish is the treatment of cleaning engines.