# Patent

## Title
Additives for diesel engines

## Abstract

The present invention relates to the use of at least 120 ppm of a nitrogen-containing detergent as a diesel fuel additive to improve the performance of a diesel engine having a high pressure fuel system.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national stage application under 35 U.S.C. 371 of co-pending International Application No. PCT/GB08/50868 filed Sep. 25, 2008 and entitled “ADDITIVES FOR DIESEL ENGINES”, which in turn claims priority to Great Britain Patent Application No. 0718862.6 filed Sep. 27, 2007, and to Great Britain Patent Application No. 0808406.3 filed May 9, 2008, all of which are incorporated by reference herein in their entirety for all purposes.
The present invention relates to additives for diesel fuel compositions. In particular the invention relates to the use of additives for diesel fuel compositions in diesel engines with high pressure fuel systems.
Due to consumer demand and legislation, diesel engines have in recent years become much more energy efficient, show improved performance and have reduced emissions.
These improvements in performance and emissions have been brought about by improvements in the combustion process. To achieve the fuel atomisation necessary for this improved combustion, fuel injection equipment has been developed which uses higher injection pressures and reduced fuel injector nozzle hole diameters. The fuel pressure at the injection nozzle is now commonly in excess of 1500 bar (1.5×108 Pa). To achieve these pressures the work that must be done on the fuel also increases the temperature of the fuel. These high pressures and temperatures can cause degradation of the fuel.
Diesel engines having high pressure fuel systems can include but are not limited to heavy duty diesel engines and smaller passenger car type diesel engines. Heavy duty diesel engines can include very powerful engines such as the MTU series 4000 diesel having 20 cylinder variants with power output up to 4300 kW or engines such as the Renault dXi 7 having 6 cylinders and a power output around 240 kW. A typical passenger car diesel engine is the Peugeot DW10 having 4 cylinders and power output of 100 kW or less depending on the variant.
In all of the diesel engines relating to this invention, a common feature is a high pressure fuel system. Typically pressures in excess of 1350 bar (1.35×108 Pa) are used but often pressures of up to 2000 bar (2×108 Pa) or more may exist.
Two non-limiting examples of such high pressure fuel systems are: the common rail injection system, in which the fuel is compressed utilizing a high-pressure pump that supplies it to the fuel injection valves through a common rail; and the unit injection system which integrates the high-pressure pump and fuel injection valve in one assembly, achieving the highest possible injection pressures exceeding 2000 bar (2×108 Pa). In both systems, in pressurizing the fuel, the fuel gets hot, often to temperatures around 100° C., or above.
In common rail systems, the fuel is stored at high pressure in the central accumulator rail or separate accumulators prior to being delivered to the injectors. Often, some of the heated fuel is returned to the low pressure side of the fuel system or returned to the fuel tank. In unit injection systems the fuel is compressed within the injector in order to generate the high injection pressures. This in turn increases the temperature of the fuel.
In both systems, fuel is present in the injector body prior to injection where it is heated further due to heat from the combustion chamber. The temperature of the fuel at the tip of the injector can be as high as 250-350° C.
Thus the fuel is stressed at pressures from 1350 bar (1.35×108 Pa) to over 2000 bar (2×108 Pa) and temperatures from around 100° C. to 350° C. prior to injection, sometimes being recirculated back within the fuel system thus increasing the time for which the fuel experiences these conditions.
A common problem with diesel engines is fouling of the injector, particularly the injector body, and the injector nozzle. Fouling may also occur in the fuel filter. Injector nozzle fouling occurs when the nozzle becomes blocked with deposits from the diesel fuel. Fouling of fuel filters may be related to the recirculation of fuel back to the fuel tank. Deposits increase with degradation of the fuel. Deposits may take the form of carbonaceous coke-like residues or sticky or gum-like residues. In some situations very high additive treat rates may lead to increased deposits. Diesel fuels become more and more unstable the more they are heated, particularly if heated under pressure. Thus diesel engines having high pressure fuel systems may cause increased fuel degradation.
The problem of injector fouling may occur when using any type of diesel fuels. However, some fuels may be particularly prone to cause fouling or fouling may occur more quickly when these fuels are used. For example, fuels containing biodiesel have been found to produce injector fouling more readily. Diesel fuels containing metallic species may also lead to increased deposits. Metallic species may be deliberately added to a fuel in additive compositions or may be present as contaminant species. Contamination occurs if metallic species from fuel distribution systems, vehicle distribution systems, vehicle fuel systems, other metallic components and lubricating oils become dissolved or dispersed in fuel.
Transition metals in particular cause increased deposits, especially copper and zinc species. These may be typically present at levels from a few ppb (parts per billion) up to 50 ppm, but it is believed that levels likely to cause problems are from 0.1 to 50 ppm, for example 0.1 to 10 ppm.
When injectors become blocked or partially blocked, the delivery of fuel is less efficient and there is poor mixing of the fuel with the air. Over time this leads to a loss in power of the engine and increased exhaust emissions and poor fuel economy.
As the size of the injector nozzle hole is reduced, the relative impact of deposit build up becomes more significant. By simple arithmetic a 5 μm layer of deposit within a 500 μm hole reduces the flow area by 4% whereas the same 5 μm layer of deposit in a 200 μm hole reduces the flow area by 9.8%.
Commercial diesel fuel compositions may include a number of additives which perform a variety of different functions. Additives may be used to improve engine performance, fuel handling, fuel stability and contaminant control. Typical additives include antioxidants to prevent oxidation and thus gum forming reactions; stability improvers to prevent sediment formation; metal deactivators to chelate to metal ions and prevent the catalysis thereby of oxidation reactions; cetane improvers to promote oxidation at higher temperatures by the generation of free radicals; dispersants or detergents to prevent deposit formation in the injection system or remove existing deposits; lubricity improvers to prevent wear; as well as corrosion inhibitors, anti-static additives, dehazers and demulsifiers, cold-flow improvers, wax anti-settling additives, anti-foams, dyes, markers, odour masks and drag reducers.
Over time those working in the field of diesel fuel additives have developed additive packages and it is well known that to achieve a certain benefit a certain amount of a certain additive should be used. Thus typical or standard treat rates are known for specific additives, and additive combinations.
Modern diesel engines including finer injector nozzles are more sensitive than previous diesel technology and current diesel fuels including current additives at current treat rates may not be suitable for use with the new engines incorporating these finer nozzles.
The present inventor has discovered that using a higher level of detergent in diesel fuel compositions may provide improved performance in diesel engines having high pressure fuel systems, compared with diesel fuel compositions of the prior art.
According to a first aspect of the present invention there is provided the use of at least 120 ppm of a nitrogen-containing detergent as a diesel fuel additive to improve the performance of a diesel engine having a high pressure fuel system.
The nitrogen-containing detergent is preferably used in the diesel fuel an amount of at least 125 ppm, preferably at least 130 ppm, more preferably at least 135 ppm, most preferably at least 140 ppm.
The nitrogen-containing detergent is preferably used in the diesel fuel in an amount up to 10000 ppm, preferably up to 5000 ppm, preferably up to 3000 ppm, more preferably up to 2000 ppm, preferably up to 1500 ppm and most preferably up to 1250 ppm.
The nitrogen-containing detergent may suitably be used in an amount of, for example, from 120 to 200 ppm, 200 to 300 ppm, 300 to 500 ppm, 500 to 750 ppm or 750 to 1000 ppm.
Preferably the present invention provides the use of a nitrogen-containing detergent as a diesel fuel additive at a concentration of from 120 to 2000 ppm, preferably 120 to 1500 ppm, more preferably 125 to 1000 ppm, preferably 130 to 600 ppm and most preferably 130 to 350 ppm.
All values of ppm given in this specification refer to parts per million by weight of the total composition.
The concentrations referred to herein refer to the concentration of neat (100%) additive. However in practice additives may be diluted prior to addition and commercially available additives are often sold as solutions or dispersions. For example, they may be sold as a 60% solution of active in aromatic solvents.
The present invention covers the use of any suitable nitrogen-containing detergent (including ashless detergent or dispersant) known in the art for use in lubricant or fuel oil.
Preferred nitrogen-containing detergents are the reaction products of a carboxylic acid-derived acylating agent and an amine.
A number of acylated, nitrogen-containing compounds having a hydrocarbyl substituent of at least 8 carbon atoms and made by reacting a carboxylic acid acylating agent with an amino compound are known to those skilled in the art. In such compositions the acylating agent is linked to the amino compound through an imido, amido, amidine or acyloxy ammonium linkage. The hydrocarbyl substituent of at least 8 carbon atoms may be in either the carboxylic acid acylating agent derived portion of the molecule or in the amino compound derived portion of the molecule, or both. Preferably, however, it is in the acylating agent portion. The acylating agent can vary from formic acid and its acylating derivatives to acylating agents having high molecular weight aliphatic substituents of up to 5,000, 10,000 or 20,000 carbon atoms. The amino compounds can vary from ammonia itself to amines typically having aliphatic substituents of up to about 30 carbon atoms, and up to 11 nitrogen atoms.
A preferred class of acylated amino compounds suitable for use in the present invention are those formed by the reaction of an acylating agent having a hydrocarbyl substituent of at least 8 carbon atoms and a compound comprising at least one primary or secondary amine group. The acylating agent may be a mono- or polycarboxylic acid (or reactive equivalent thereof) for example a substituted succinic, phthalic or propionic acid and the amino compound may be a polyamine or a mixture of polyamines, for example a mixture of ethylene polyamines. Alternatively the amine may be a hydroxyalkyl-substituted polyamine. The hydrocarbyl substituent in such acylating agents preferably comprises at least 10, more preferably at least 12, for example 30 or 50 carbon atoms. It may comprise up to about 200 carbon atoms. Preferably the hydrocarbyl substituent of the acylating agent has a number average molecular weight (Mn) of between 170 to 2800, for example from 250 to 1500, preferably from 500 to 1500 and more preferably 500 to 1100. An Mn of 700 to 1300 is especially preferred. In a particularly preferred embodiment, the hydrocarbyl substituent has a number average molecular weight of 700-1000, preferably 700-850 for example 750.
Illustrative of hydrocarbyl substituent based groups containing at least eight carbon atoms are n-octyl, n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chloroctadecyl, triicontanyl, etc. The hydrocarbyl based substituents may be made from homo- or interpolymers (e.g. copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, for example ethylene, propylene, butane-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. Preferably these olefins are 1-monoolefins. The hydrocarbyl substituent may also be derived from the halogenated (e.g. chlorinated or brominated) analogs of such homo- or interpolymers. Alternatively the substituent may be made from other sources, for example monomeric high molecular weight alkenes (e.g. 1-tetra-contene) and chlorinated analogs and hydrochlorinated analogs thereof, aliphatic petroleum fractions, for example paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogs thereof, white oils, synthetic alkenes for example produced by the Ziegler-Natta process (e.g. poly(ethylene) greases) and other sources known to those skilled in the art. Any unsaturation in the substituent may if desired be reduced or eliminated by hydrogenation according to procedures known in the art.
The term “hydrocarbyl” as used herein denotes a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly aliphatic hydrocarbon character. Suitable hydrocarbyl based groups may contain non-hydrocarbon moieties. For example they may contain up to one non-hydrocarbyl group for every ten carbon atoms provided this non-hydrocarbyl group does not significantly alter the predominantly hydrocarbon character of the group. Those skilled in the art will be aware of such groups, which include for example hydroxyl, halo (especially chloro and fluoro), alkoxyl, alkyl mercapto, alkyl sulphoxy, etc. Preferred hydrocarbyl based substituents are purely aliphatic hydrocarbon in character and do not contain such groups.
The hydrocarbyl-based substituents are preferably predominantly saturated, that is, they contain no more than one carbon-to-carbon unsaturated bond for every ten carbon-to-carbon single bonds present. Most preferably they contain no more than one carbon-to-carbon non-aromatic unsaturated bond for every 50 carbon-to-carbon bonds present.
Preferred hydrocarbyl-based substituents are poly-(isobutene)s known in the art.
Conventional polyisobutenes and so-called “highly-reactive” polyisobutenes are suitable for use in the invention. Highly reactive polyisobutenes in this context are defined as polyisobutenes wherein at least 50%, preferably 70% or more, of the terminal olefinic double bonds are of the vinylidene type as described in EP0565285. Particularly preferred polyisobutenes are those having more than 80 mol% and up to 100 mol% of terminal vinylidene groups such as those described in EP1344785.
Amino compounds useful for reaction with these acylating agents include the following:
(1) polyalkylene polyamines of the general formula:

(R3)2N[U—N(R3)]nR3 

wherein each R3 is independently selected from a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group containing up to about 30 carbon atoms, with proviso that at least one R3 is a hydrogen atom, n is a whole number from 1 to 10 and U is a C1-18 alkylene group. Preferably each R3 is independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl and isomers thereof. Most preferably each R3 is ethyl or hydrogen. U is preferably a C1-4 alkylene group, most preferably ethylene.
(2) heterocyclic-substituted polyamines including hydroxyalkyl-substituted polyamines wherein the polyamines are as described above and the heterocyclic substituent is selected from nitrogen-containing aliphatic and aromatic heterocycles, for example piperazines, imidazolines, pyrimidines, morpholines, etc.
(3) aromatic polyamines of the general formula:

Ar(NR32)y 

wherein Ar is an aromatic nucleus of 6 to 20 carbon atoms, each R3 is as defined above and y is from 2 to 8.
Specific examples of polyalkylene polyamines (1) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tri(tri-methylene)tetramine, pentaethylenehexamine, hexaethylene-heptamine, 1,2-propylenediamine, and other commercially available materials which comprise complex mixtures of polyamines. For example, higher ethylene polyamines optionally containing all or some of the above in addition to higher boiling fractions containing 8 or more nitrogen atoms etc. Specific examples of hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylene diamine, N,N′-bis(2-hydroxyethyl)ethylene diamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Specific examples of the heterocyclic-substituted polyamines (2) are N-2-aminoethyl piperazine, N-2 and N-3 amino propyl morpholine, N-3(dimethyl amino)propyl piperazine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,4-bis(2-aminoethyl)piperazine, 1-(2-hydroxy ethyl)piperazine, and 2-heptadecyl-1-(2-hydroxyethyl)-imidazoline, etc. Specific examples of the aromatic polyamines (3) are the various isomeric phenylene diamines, the various isomeric naphthalene diamines, etc.
Many patents have described useful acylated nitrogen compounds including U.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746; 3,310,492; 3,341,542; 3,444,170; 3,455,831; 3,455,832; 3,576,743; 3,630,904; 3,632,511; 3,804,763, 4,234,435 and U.S. Pat. No. 6,821,307.
A preferred acylated nitrogen-containing compound of this class is that made by reacting a poly(isobutene)-substituted succinic acid-derived acylating agent (e.g., anhydride, acid, ester, etc.) wherein the poly(isobutene) substituent has between about 12 to about 200 carbon atoms with a mixture of ethylene polyamines having 3 to about 9 amino nitrogen atoms, preferably about 3 to about 8 nitrogen atoms, per ethylene polyamine and about 1 to about 8 ethylene groups. These acylated nitrogen compounds are formed by the reaction of a molar ratio of acylating agent: amino compound of from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 2:1 to 1:2 and most preferably from 2:1 to 1:1. In especially preferred embodiments, the acylated nitrogen compounds are formed by the reaction of acylating agent to amino compound in a molar ratio of from 1.8:1 to 1:1.2, preferably from 1.6:1 to 1:1.2, more preferably from 1.4:1 to 1:1.1 and most preferably from 1.2:1 to 1:1. This type of acylated amino compound and the preparation thereof is well known to those skilled in the art and are described in the above-referenced US patents.
Another type of acylated nitrogen compound belonging to this class is that made by reacting the afore-described alkylene amines with the afore-described substituted succinic acids or anhydrides and aliphatic mono-carboxylic acids having from 2 to about 22 carbon atoms. In these types of acylated nitrogen compounds, the mole ratio of succinic acid to mono-carboxylic acid ranges from about 1:0.1 to about 1:1. Typical of the monocarboxlyic acid are formic acid, acetic acid, dodecanoic acid, butanoic acid, oleic acid, stearic acid, the commercial mixture of stearic acid isomers known as isostearic acid, tolyl acid, etc. Such materials are more fully described in U.S. Pat. Nos. 3,216,936 and 3,250,715.
A further type of acylated nitrogen compound suitable for use in the present invention is the product of the reaction of a fatty monocarboxylic acid of about 12-30 carbon atoms and the afore-described alkylene amines, typically, ethylene, propylene or trimethylene polyamines containing 2 to 8 amino groups and mixtures thereof. The fatty mono-carboxylic acids are generally mixtures of straight and branched chain fatty carboxylic acids containing 12-30 carbon atoms. Fatty dicarboxylic acids could also be used. A widely used type of acylated nitrogen compound is made by reacting the afore-described alkylene polyamines with a mixture of fatty acids having from 5 to about 30 mole percent straight chain acid and about 70 to about 95 percent mole branched chain fatty acids. Among the commercially available mixtures are those known widely in the trade as isostearic acid. These mixtures are produced as a by-product from the dimerization of unsaturated fatty acids as described in U.S. Pat. Nos. 2,812,342 and 3,260,671.
The branched chain fatty acids can also include those in which the branch may not be alkyl in nature, for example phenyl and cyclohexyl stearic acid and the chloro-stearic acids. Branched chain fatty carboxylic acid/alkylene polyamine products have been described extensively in the art. See for example, U.S. Pat. Nos. 3,110,673; 3,251,853; 3,326,801; 3,337,459; 3,405,064; 3,429,674; 3,468,639; 3,857,791. These patents are referenced for their disclosure of fatty acid/polyamine condensates for their use in lubricating oil formulations.
The diesel fuel composition used in the present invention may comprise a petroleum-based fuel oil, especially a middle distillate fuel oil. Such distillate fuel oils generally boil within the range of from 110° C. to 500° C., e.g. 150° C. to 400° C. The diesel fuel may comprise atmospheric distillate or vacuum distillate, cracked gas oil, or a blend in any proportion of straight run and refinery streams such as thermally and/or catalytically cracked and hydro-cracked distillates.
The diesel fuel composition used in the present invention may comprise non-renewable Fischer-Tropsch fuels such as those described as GTL (gas-to-liquid) fuels, CTL (coal-to-liquid) fuels and OTL (oil sands-to-liquid).
The diesel fuel composition used in the present invention may comprise a renewable fuel such as a biofuel composition or biodiesel composition.
The diesel fuel composition may comprise 1st generation biodiesel. First generation biodiesel contains esters of, for example, vegetable oils, animal fats and used cooking fats. This form of biodiesel may be obtained by transesterification of oils, for example rapeseed oil, soybean oil, safflower oil, palm 25 oil, corn oil, peanut oil, cotton seed oil, tallow, coconut oil, physic nut oil (Jatropha), sunflower seed oil, used cooking oils, hydrogenated vegetable oils or any mixture thereof, with an alcohol, usually a monoalcohol, in the presence of a catalyst.
The diesel fuel composition may comprise second generation biodiesel. Second generation biodiesel is derived from renewable resources such as vegetable oils and animal fats and processed, often in the refinery, often using hydroprocessing such as the H-Bio process developed by Petrobras. Second generation biodiesel may be similar in properties and quality to petroleum based fuel oil streams, for example renewable diesel produced from vegetable oils, animal fats etc. and marketed by ConocoPhillips as Renewable Diesel and by Neste as NExBTL.
The diesel fuel composition used in the present invention may comprise third generation biodiesel. Third generation biodiesel utilises gasification and Fischer-Tropsch technology including those described as BTL (biomass-to-liquid) fuels. Third generation biodiesel does not differ widely from some second generation biodiesel, but aims to exploit the whole plant (biomass) and thereby widens the feedstock base.
The diesel fuel composition may contain blends of any or all of the above diesel fuel compositions.
In some embodiments the diesel fuel composition used in the present invention may be a blended diesel fuel comprising bio-diesel. In such blends the bio-diesel may be present in an amount of, for example up to 0.5%, up to 1%, up to 2%, up to 3%, up to 4%, up to 5%, up to 10%, up to 20%, up to 30%, up to 40%, up to 50%, up to 60%, up to 70%, up to 80%, up to 90%, up to 95% or up to 99%.
In some embodiments the diesel fuel composition may comprise a secondary fuel, for example ethanol. Preferably however the diesel fuel composition does not contain ethanol.
Preferably, the diesel fuel has a sulphur content of at most 0.05% by weight, more preferably of at most 0.035% by weight, especially of at most 0.015%. Fuels with even lower levels of sulphur are also suitable such as, fuels with less than 50 ppm sulphur by weight, preferably less than 20 ppm, for example 10 ppm or less.
Commonly when present, metal-containing species will be present as a contaminant, for example through the corrosion of metal and metal oxide surfaces by acidic species present in the fuel or from lubricating oil. In use, fuels such as diesel fuels routinely come into contact with metal surfaces for example, in vehicle fuelling systems, fuel tanks, fuel transportation means etc. Typically, metal-containing contamination will comprise transition metals such as zinc, iron and copper and others such as lead.
In addition to metal-containing contamination which may be present in diesel fuels there are circumstances where metal-containing species may deliberately be added to the fuel. For example, as is known in the art, metal-containing fuel-borne catalyst species may be added to aid with the regeneration of particulate traps. Such catalysts are often based on metals such as iron, cerium, Group I and Group II metals e.g., calcium and strontium, either as mixtures or alone. Also used are platinum and manganese. The presence of such catalysts may also give rise to injector deposits when the fuels are used in diesel engines having high pressure fuel systems.
Metal-containing contamination, depending on its source, may be in the form of insoluble particulates or soluble compounds or complexes. Metal-containing fuel-borne catalysts are often soluble compounds or complexes or colloidal species.
In some embodiments, the metal-containing species comprises a fuel-borne catalyst.
In some embodiments, the metal-containing species comprises zinc.
Typically, the amount of metal-containing species in the diesel fuel, expressed in terms of the total weight of metal in the species, is between 0.1 and 50 ppm by weight, for example between 0.1 and 10 ppm by weight, based on the weight of the diesel fuel.
In embodiments in which the fuel comprises 1 to 20, for example 5 to 15% bio-diesel, the present invention preferably provides the use of at least 150 ppm, preferably at least 200 ppm, for example at least 300 ppm, at least 350 ppm or at least 500 ppm of a nitrogen-containing detergent as an additive to improve the performance of a diesel engine having a high pressure fuel system. Suitably treat rates of 200 to 600 ppm may be used, for example from 300 to 600 ppm.
The diesel fuel composition used in the present invention may include one or more further additives such as those which are commonly found in diesel fuels. These include, for example, antioxidants, dispersants, detergents, wax anti-settling agents, cold flow improvers, cetane improvers, dehazers, stabilisers, demulsifiers, antifoams, corrosion inhibitors, lubricity improvers, dyes, markers, combustion improvers, metal deactivators, odour masks, drag reducers and conductivity improvers.
In particular, the composition used in the present invention may further comprise one or more additives known to improve the performance of diesel engines having high pressure fuel systems. Such additives are known to those skilled in the art and include, for example, the compounds described in EP 1900795, EP 1887074 and EP 1884556.
Suitably the diesel fuel composition may include an additive comprising a salt formed by the reaction of a carboxylic acid with a di-n-butylamine or tri-n-butylamine. Suitably the fatty acid is of the formula [R′(COOH)x]y′, where each R′ is a independently a hydrocarbon group of between 2 and 45 carbon atoms, and x is an integer between 1 and 4.
Preferably R′ is a hydrocarbon group of 8 to 24 carbon atoms, more preferably 12 to 20 carbon atoms. Preferably, x is 1 or 2, more preferably x is 1. Preferably, y is 1, in which case the acid has a single R′ group. Alternatively, the acid may be a dimer, trimer or higher oligomer acid, in which case y will be greater than 1 for example 2, 3 or 4 or more. R′ is suitably an alkyl or alkenyl group which may be linear or branched. Examples of carboxylic acids which may be used in the present invention include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, neodecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, caproleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, coconut oil fatty acid, soy bean fatty acid, tall oil fatty acid, sunflower oil fatty acid, fish oil fatty acid, rapeseed oil fatty acid, tallow oil fatty acid and palm oil fatty acid. Mixtures of two or more acids in any proportion are also suitable. Also suitable are the anhydrides of carboxylic acids, their derivatives and mixtures thereof. In a preferred embodiment, the carboxylic acid comprises tall oil fatty acid (TOFA). It has been found that TOFA with a saturate content of less than 5% by weight is especially suitable.
When such additives are present in diesel fuel as the only means of reducing injector deposits they are typically added at treat rates of 20-400 ppm eg 20-200 ppm.
The treat rate of such additives would typically be less than the upper limit of these ranges eg less than 400 ppm or less than 200 ppm and possibly lower than the lower limit of this range eg less than 20 ppm, for example down to 5 ppm or 2 ppm, when used in combination with the performance enhancing additives of the present invention.
Suitably the diesel fuel composition may include an additive comprising the reaction product between a hydrocarbyl-substituted succinic acid or anhydride and hydrazine.
Preferably, the hydrocarbyl group of the hydrocarbyl-substituted succinic acid or anhydride comprises a C8-C36 group, preferably a C8-C18 group. Non-limiting examples include dodecyl, hexadecyl and octadecyl. Alternatively, the hydrocarbyl group may be a polyisobutylene group with a number average molecular weight of between 200 and 2500, preferably between 800 and 1200. Mixtures of species with different length hydrocarbyl groups are also suitable, e.g. a mixture of C16-C18 groups.
The hydrocarbyl group is attached to a succinic acid or anhydride moiety using methods known in the art. Additionally, or alternatively, suitable hydrocarbyl-substituted succinic acids or anhydrides are commercially available e.g. dodecylsuccinic anhydride (DDSA), hexadecylsuccinic anhydride (HDSA), octadecylsuccinic anhydride (ODSA) and polyisobutylsuccinic anhydride (PIBSA).
Hydrazine has the formula:

NH2—NH2 

Hydrazine may be hydrated or non-hydrated. Hydrazine monohydrate is preferred.
The reaction between the hydrocarbyl-substituted succinic acid or anhydride and hydrazine produces a variety of products, such as is disclosed in EP 1887074. It is believed to be preferable for good detergency that the reaction product contains a significant proportion of species with relatively high molecular weight. It is believed—without the matter having been definitively determined yet, to the best of our knowledge—that a major high molecular weight product of the reaction is an oligomeric species predominantly of the structure:




where n is an integer and greater than 1, preferably between 2 and 10, more preferably between 2 and 7, for example 3, 4 or 5. Each end of the oligomer may be capped by one or more of a variety of groups. Some possible examples of these terminal groups include:




Alternatively, the oligomeric species may form a ring having no terminal groups:




When such additives are present in diesel fuel as the only means of reducing injector deposits they are typically added at treat rates of 10-500 ppm eg 20-100 ppm.
The treat rate of such additives would typically be less than the upper limit of these ranges eg less than 500 ppm or less than 100 ppm and possibly lower than the lower limit of this range eg less than 20 ppm or less than 10 ppm, for example down to 5 ppm or 2 ppm, when used in combination with the performance enhancing additives of this invention.
Suitably the diesel fuel composition may include an additive comprising at least one compound of formula (I) and/or formula (II):




wherein each Ar independently represents an aromatic moiety having 0 to 3 substituents selected from the group consisting of alkyl, alkoxy, alkoxyalkyl, aryloxy, aryloxyalkyl, hydroxy, hydroxyalkyl, halo and combinations thereof;
each L is independently a linking moiety comprising a carbon-carbon single bond or a linking group;
each Y is independently —OR1′′ or a moiety of the formula H(O(CR12)n)yX—, wherein X is selected from the group consisting of (CR12)2, O and S: R1 and R1′ are each independently selected from H, C1 to C6 alkyl and aryl; R1′′ is selected from C1 to C100 alkyl and aryl; z is 1 to 10; n is 0 to 10 when X is (CR12)2, and 2 to 10 when X is O or S; and y is 1 to 30;
each a is independently 0 to 3, with the proviso that at least one Ar moiety bears at least one group Y; and m is 1 to 100;




wherein:
each Ar′ independently represents an aromatic moiety having 0 to 3 substituents selected from the group consisting of alkyl, alkoxy, alkoxyalkyl, hydroxy, hydroxyalkyl, acyloxy, acyloxyalkyl, acyloxyalkoxy, aryloxy, aryloxyalkyl, aryloxyalkoxy, halo and combinations thereof;
each L′ is independently a linking moiety comprising a carbon-carbon single bond or linking group;
each Y′ is independently a moiety of the formula ZO— or Z(O(CR22)n′)y′, X′—, wherein X′ is selected from the group consisting of (CR2′2)z′, O and S; R2 and R2′ are each independently selected from H, C1 to C6 alkyl and aryl z′ is 1 to 10; n′ is 0 to 10 when X′ is (CR2′2)z, and 2 to 10 when X′ is O or S; y is 1 to 30; Z is H, an acyl group, a polyacyl group, a lactone ester group, an acid ester group, an alkyl group or an aryl group;
each a′ is independently 0 to 3, with the proviso that at least one Ar′ moiety bears at least one group Y′ in which Z is not H; and m′ is 1 to 100.
When such additives are present in diesel fuel as the only means of reducing injector deposits they are typically added at treat rates of 50-300 ppm.
The treat rate of such additives would typically be less than the upper limit of these ranges eg less than 300 ppm and possibly lower than the lower limit of this range eg less than 50 ppm, for example down to 20 ppm or 10 ppm, when used in combination with the performance enhancing additives of this invention.
Suitably the diesel fuel composition may include an additive comprising a quaternary ammonium salt which comprises the reaction product of (a) a hydrocarbyl-substituted acylating agent and a compound having an oxygen or nitrogen atom capable of condensing with said acylating agent and further having a tertiary amino group; and (b) a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen wherein the quaternizing agent is selected from the group consisting of dialkyl sulphates, benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combination with an acid or mixtures thereof.
Examples of quaternary ammonium salt and methods for preparing the same are described in the following patents, which are hereby incorporated by reference, U.S. Pat. No. 4,253,980, U.S. Pat. No. 3,778,371, U.S. Pat. No. 4,171,959, U.S. Pat. No. 4,326,973, U.S. Pat. No. 4,338,206, and U.S. Pat. No. 5,254,138.
Suitable acylating agents and hydrocarbyl subsituents are as previously defined in this specification.
Examples of the nitrogen or oxygen containing compounds capable of condensing with the acylating agent and further having a tertiary amino group can include but are not limited to: N,N-dimethyl-aminopropylamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-amino ethylamine. The nitrogen or oxygen containing compounds capable of condensing with the acylating agent and further having a tertiary amino group can further include amino alkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldi-propylamine, and 3′3-aminobis(N,N-dimethylpropylamine). Other types of nitrogen or oxygen containing compounds capable of condensing with the acylating agent and having a tertiary amino group include alkanolamines including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine and N,N,N-tris(hydroxymethyl)amine.
The composition used in the present invention may contain a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen wherein the quaternizing agent is selected from the group consisting of dialkyl sulphates, alkyl halides, benzyl halides, hydrocarbyl substituted carbonates; and hydrocarbyl epoxides in combination with an acid or mixtures thereof.
The quaternizing agent can include halides, such as chloride, iodide or bromide; hydroxides; sulphonates; bisulphites, alkyl sulphates, such as dimethyl sulphate; sulphones; phosphates; C1-12 alkylphosphates; di C1-12 alkylphosphates; borates; C1-12 alkylborates; nitrites; nitrates; carbonates; bicarbonates; alkanoates; O,O-di C1-12 alkyldithiophosphates; or mixtures thereof.
In one embodiment the quaternizing agent may be derived from dialkyl sulphates such as dimethyl sulphate, N-oxides, sulphones such as propane and butane sulphone; alkyl, acyl or aralkyl halides such as methyl and ethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (or alkyl) substituted carbonates. If the acyl halide is benzyl chloride, the aromatic ring is optionally further substituted with alkyl or alkenyl groups. The hydrocarbyl (or alkyl) groups of the hydrocarbyl substituted carbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atoms per group. In one embodiment the hydrocarbyl substituted carbonates contain two hydrocarbyl groups that may be the same or different. Examples of suitable hydrocarbyl substituted carbonates include dimethyl or diethyl carbonate.
In another embodiment the quaternizing agent can be a hydrocarbyl epoxide, as represented by the following formula, in combination with an acid:




wherein R1, R2, R3 and R4 can be independently H or a C1-50 hydrocarbyl group.
Examples of hydrocarbyl epoxides can include styrene oxide, ethylene oxide, propylene oxide, butylene oxide, stilbene oxide and C2-50 epoxide.
When such quaternary ammonium salt additives are present in diesel fuel as the only means of reducing injector deposits they are typically added at treat rates of 5-500 ppm eg 10-100 ppm.
The treat rate of such additives would typically be less than the upper limit of these ranges eg less than 500 ppm or less than 100 ppm and possibly lower than the lower limit of this range eg less than 10 ppm or less than 5 ppm, for example down to 5 ppm or 2 ppm, when used in combination with the performance enhancing additives of this invention.
In some embodiments the diesel fuel composition used in the present invention further comprises a metal deactivating compound. Any metal deactivating compound known to those skilled in the art may be used and include, for example, the substituted triazole compounds of figure III wherein R and R′ are independently selected from an optionally substituted alkyl group or hydrogen.




Preferred metal deactivating compounds are those of formula IV:




wherein R1, R2 and R3 are independently selected from an optionally-substituted alkyl group or hydrogen, preferably an alkyl group from 1 to 4 carbon atoms or hydrogen. R1 is preferably hydrogen, R2 is preferably hydrogen and R3 is preferably methyl. n is an integer from 0 to 5, most preferably 1.
A particularly preferred metal deactivator is N,N′-disalicyclidene-1,2-diaminopropane, and has the formula shown in figure V.




Another preferred metal deactivating compound is shown in figure VI:




The metal deactivating compound is preferably present in an amount of less than 100 ppm, and more preferably less than 50 ppm, preferably less than 30 ppm, more preferably less than 20, preferably less than 15, preferably less than 10 and more preferably less than 5 ppm. The metal deactivator is preferably present as an amount of from 0.0001 to 50 ppm, preferably 0.001 to 20, more preferably 0.01 to 10 ppm and most preferably 0.1 to 5 ppm.
In some embodiments the diesel fuel composition used in the present invention further comprises an antioxidant.
Any known antioxidant additive may be used. Preferred antioxidants are phenolic antioxidants and phenylenediamine antioxidants. Also useful are naturally occurring antioxidants for example tocopherol (vitamin E and derivatives therefore); and nitroxide compounds, for example 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-TEMPO, 4-oxo-TEMPO etc.
By phenolic antioxidant additive we mean to include any compound which contains a phenol moiety i.e., a benzene ring which is substituted with a hydroxyl group. This may be a very simple compound, for example a benzene diol, alkyl substituted phenol or a benzene triol. Alternatively the phenolic antioxidant may be part of a more complex molecule. It may include two phenol moieties, for example, see the compounds disclosed in US 2006/0219979.
Suitable phenolic antioxidant compounds for use in the present invention include those of formula VII:




wherein R1 is selected from an optionally substituted alkyl or alkenyl group, an aryl group, an ester, a carboxylic acid, an aldehyde, a ketone, an ether, an alcohol, an amine or an amide; R2 and R3 are independently selected from hydrogen, an optionally substituted alkyl or alkenyl group, an aryl group, an ester group, a ketone, an aldehyde, a carboxylic acid, an ether, an alcohol, an amine or an amide; and n is an integer from 1 to 5.
Preferably R1 is an alkyl group, preferably having 1 to 9 carbon atoms, and may be straight chained or branched. Preferably R1 is selected from methyl, ethyl, isopropyl, and tertiarybutyl. R1 and R2 may together form a cyclic substituent, either alkyl or aryl. R2 and R3 are preferably hydrogen or an alkyl group having 1 to 9 carbon atoms. Preferably R2 and R3 are independently selected from hydrogen, methyl, ethyl, tertiarybutyl and isopropyl. Preferably n is 1, 2 or 3.
Preferred phenolic antioxidant compounds for use in the present invention are substituted benzene compounds having 1 or more hydroxy substituents. Examples include tertiarybutylhydroquinone, pyrogallol, pyrocatechol 2,6-di-tert-butyl-4-methylphenol (BHT), propylgallate and tertiarybutylcatechol.
Preferred phenylenediamine antioxidants suitable for use in the present invention include those of formula VIII:




wherein R1, R2, R3, R4, R5, R6 and R7 are independently selected from an optionally substituted alkyl or alkenyl group, an aryl group, an ester, a carboxylic acid, an aldehyde, a ketone, an ether, an alcohol, an amine or an amide. Preferably R1 is hydrogen. Preferably R3 is hydrogen. Preferably R2 is an alkyl group, preferably having 1-10 carbon atoms. More Preferably R2 is an alkyl group having 1-5 carbon atoms. Preferably R2 is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl and tertiarybutyl. Most preferably R2 is isopropyl or secbutyl. Preferably R4 is an alkyl group, preferably having 1-10 carbon atoms. More preferably R4 is an alkyl group having 1-5 carbon atoms. R4 is preferably selected from methyl, ethyl, propyl, isopropyl, secbutyl, butyl, tertiarybutyl and isobutyl. Most preferably R4 is isopropyl or sec butyl.
R5, R6 and R7 are preferably selected from hydrogen or alkyl groups, more preferably from hydrogen and alkyl groups having 1-10 carbon atoms, more preferably from hydrogen and alkyl groups having 1-5 carbon atoms. Preferably R5, R6 and R7 are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tertiarybutyl and isobutyl. Most preferably R5 is hydrogen. Most preferably R6 is hydrogen. Most preferably R7 is hydrogen.
In a preferred embodiment however the antioxidant component of the present invention is a phenolic antioxidant compound especially a hindered phenolic antioxidant compound. By hindered phenolic antioxiodant, we refer to a phenol compound which is preferably ortho-substituted. It may also be para substituted.
Suitably the antioxidant additive is present in an amount of at least 1 ppm, more preferably at least 5 ppm, preferably at least 10 ppm, more preferably at least 15 ppm and most preferably at least 20 ppm (by weight). The phenolic antioxidant may be present in the fuel composition in an amount of up to 20,000 ppm, preferably up to 10,000 ppm, more preferably up to 5,000 ppm, preferably up to 1,000 ppm and most preferably up to 500 ppm.
The improvement in performance of the diesel engine having a high pressure fuel system may be measured by a number of ways.
One of the ways in which the improvement in performance can be measured is by measuring the power loss in a controlled engine test, for example as described in relation to Example 3.
Suitably the use according to the present invention may be assessed by measuring the improvement in performance, as determined by a reduction in power loss of the engine.
Suitably the use according to the present invention may be assessed by measuring the improvement in performance, as determined by a reduction in deposits on the injectors of the engine.
Use of the performance enhancing additives of the present invention in this test provides a fuel giving a power loss of less than 10%, preferably less than 5%, preferably less than 4% for example less than 3%, less than 2% or less than 1%.
Preferably the use of the present invention reduces the power loss of the engine by at least 2%, preferably at least 10%, preferably at least 25%, more preferably at least 50% and most preferably at least 80% compared to an engine using the base fuel.
The improvement in performance of the diesel engine having a high pressure fuel system may be measured by an improvement in fuel economy.
Improvement in performance may also be assessed by considering the extent to which the use of the performance enhancing additive preferably reduces the amount of deposit on the injector of an engine having a high pressure fuel system.
Direct measurement of deposit build up is not usually undertaken, but is usually inferred from the power loss mentioned earlier or fuel flow rates through the injector. An alternative measure of deposits can be obtained by removing the injectors from the engine and placing in a test rig. A suitable test rig is the DIT 31. The DIT31 has three methods of testing a fouled injector: by measuring the back pressure, the pressure drop or the injector time.
To measure the back pressure, the injector is pressurised to 1000 bar (108 Pa). The pressure is allowed to fall and the time taken for the pressure to drop between 2 set points is measured. This tests the integrity of the injector which should maintain the pressure for a set period. If there is any failure in performance, the pressure will fall more rapidly. This is a good indication of internal fouling, particularly by gums. For example, a typical passenger car injector may take a minimum of 10 seconds for the pressure to drop between the two set points.
To measure the pressure drop, the injector is pressurised to 1000 bar (108 Pa). The pressure is allowed to fall and at a set point (750 bar-7.5×107 Pa) fires. The drop in pressure during the firing period is measured and is compared to a standard. For a typical passenger car injector this may be 80 bar (8×106 Pa). Any blockage in the injector will cause a lower pressure drop than the standard.
During the pressure drop measurement the time that the injector opens for is measured. For typical passenger car injectors this may be 10 ms+/−1. Any deposit may impinge this opening time causing the pressure drop to be affected. Thus a fouled injector may have a shortened opening time as well as a lower pressure drop.
The present invention is particularly useful in the reduction of deposits on injectors of engines operating at high pressures and temperatures in which fuel may be recirculated and which comprise a plurality of fine apertures through which the fuel is delivered to the engine. The present invention finds utility in engines for heavy duty vehicles and passenger vehicles. Passenger vehicles incorporating a high speed direct injection (or HSDI) engine may for example benefit from the present invention.
The use in accordance with the invention may improve the performance of the engine by reducing the deposits on an injector having an aperture with a diameter of less than 500 μm, preferably less than 200 μm, more preferably less than 150 μm. In some embodiments the use may improve the performance of the engine by reducing deposits on an injector with an aperture having a diameter less than 100 μm, preferably less than 80 μm. The use may improve the performance of an engine in which the injector has more than one aperture, for example more than 4 apertures, for example 6 or more apertures.
Within the injector body, clearances of only 1-2 μm exist between moving parts and there have been reports of engine problems in the field caused by injectors sticking and particularly injectors sticking open. Control of deposits in this area can be very important.
The use in accordance with the invention may improve the performance of the engine by reducing deposits including gums and lacquers within the injector body.
The use in accordance with the invention may also improve the performance of the engine by reducing deposits in the vehicle fuel filter.
A reduction of deposits in a vehicle fuel filter may be measured quantitatively or qualitatively. In some cases this may only be determined by inspection of the filter once the filter has been removed. In other cases, the level of deposits may be estimated during use.
Many vehicles are fitted with a fuel filter which may be visually inspected during use to determine the level of solids build up and the need for filter replacement. For example, one such system uses a filter canister within a transparent housing allowing the filter, the fuel level within the filter and the degree of filter blocking to be observed.
It has been surprisingly been found that when using the fuel compositions of the present invention the level of deposits in the fuel filter are considerably reduced compared with fuel compositions of the prior art. This allows the filter to be changed much less frequently and can ensure that fuel filters do not fail between service intervals. Thus the use of the present invention may lead to reduced maintenance costs.
Suitably the use of the present invention allows the interval between filter replacement to be extended, suitably by at least 5%, preferably at least 10%, more preferably at least 20%, for example at least 30% or at least 50%.
In Europe the Co-ordinating European Council for the development of performance tests for transportation fuels, lubricants and other fluids (the industry body known as CEC), has developed a new test, named CEC F-98-08, to assess whether diesel fuel is suitable for use in engines meeting new European Union emissions regulations known as the “Euro 5” regulations. The test is based on a Peugeot DW10 engine using Euro 5 injectors, and will hereinafter be referred to as the DW10 test. It will be further described in the context of the examples.
Preferably the use of the present invention leads to reduced deposits as measured in the DW10 test.
Before the priority date of this application, the inventor used the basic procedure for the DW10 test as available at that time and found that the use of the present invention in a diesel fuel composition resulted in a reduction in power loss compared with the same fuel not containing the performance enhancing additive. Details of the test method are given in Example 3.
In addition to the prevention or reduction of the occurrence of injector fouling as described above, the present inventor has also found that compositions of the present invention may be used to remove some or all of the deposits which have already formed on injectors. This is a further way by which an improvement in performance may be measured.
Thus, the present invention further provides the use of a diesel fuel composition of the first aspect to remove deposits formed in a high pressure diesel engine.
Deposits on injectors of an engine having a high pressure fuel system may also be measured using a hot liquid process simulator (or HLPS). This equipment allows the fouling of a metallic component, typically a steel or aluminium rod to be measured.
The HLPS equipment, which is generally known to those skilled in the art, includes a fuel reservoir from which fuel is pumped under pressure and passed over a heated stainless steel tube. The level of deposit on the tube after a certain period can then be measured. This is considered a good way of predicting how a much fuel would deposit on an injector. The equipment was modified to allow fuel to recirculate.
Thus the present invention provides the use of a greater than 120 ppm of a nitrogen-containing detergent reduce the deposits from a diesel fuel in the fuel injection system. This may be measured with a hot liquid process simulator for example using the method as defined in example 2.
Although the present invention provides improved performance of diesel engines having high pressure fuel systems, it may also be used with traditional diesel engines. This is important because a single fuel must be provided that can be used in new engines and older vehicles.
Any feature of the invention may be combined with any other feature, where appropriate.
The invention will now be further defined with reference to the following non-limiting examples. In these examples the terms “inv” denotes examples in accordance with the invention, “ref” denotes an example showing the properties of a base fuel and “comp” denotes comparative examples, not of the invention. However it should be noted that this is for assistance of the reader only and that the final test is whether examples fall within the scope of any actual or potential claim herein. In the examples which follow the values given in parts per million (ppm) for treat rates denote active agent amount, not the amount of a formulation as added, and containing an active agent.


Example 1
Diesel fuel compositions were prepared comprising the additives listed in Table 1, added to aliquots all drawn from a common batch of a diesel base fuel containing 1 ppm zinc (as zinc neodecanoate).









TABLE 1






Fuel
A



Composition
(ppm active)








1 (ref)
—



2 (comp)
48



3 (comp)
96



4 (inv)
144



5 (inv)
192









Additive A is a 60% active ingredient solution (in aromatic solvent) of a polyisobutenyl succinimide obtained from the condensation reaction of a polyisobutenyl succinic anhydride derived from polyisobutene of Mn approximately 750 with a polyethylene polyamine mixture of average composition approximating to tetraethylene pentamine.
The diesel base fuel was RF06. Its specification is set out in Table 2 below:









TABLE 2








Limits












Property
Units
Min
Max
Method














Cetane Number

52.0
54.0
EN ISO 5165


Density at 15° C.
kg/m3
833
837
EN ISO 3675


Distillation






50% v/v Point
° C.
245
—



95% v/v Point
° C.
345
350



FBP
° C.
—
370



Flash Point
° C.
55
—
EN 22719


Cold Filter Plugging
° C.
—
−5
EN 116


Point






Viscosity at 40° C.
mm2/sec
2.3
3.3
EN ISO 3104


Polycyclic Aromatic
% m/m
3.0
6.0
IP 391


Hydrocarbons






Sulphur Content
mg/kg
—
10
ASTM D 5453


Copper Corrosion

—
1
EN ISO 2160


Conradson Carbon
% m/m
—
0.2
EN ISO 10370


Residue on 10%






Dist. Residue






Ash Content
% m/m
—
0.01
EN ISO 6245


Water Content
% m/m
—
0.02
EN ISO 12937


Neutralisation
mg KOH/g
—
0.02
ASTM D 974


(Strong Acid) Number






Oxidation Stability
mg/mL
—
0.025
EN ISO 12205


HFRR (WSD1, 4)
μm
—
400
CEC F-06-A-96










Fatty Acid Methyl

prohibited



Ester









Example 2
Each of the fuel compositions prepared according to example 1 was tested using the Hot Liquid Process Simulator (HLPS) equipment. In this test 800 ml of fuel is pressurised to 500 psi (3.44×106 Pa) and flowed over a steel tube heated to 270° C. The test duration is 5 hours. The test method has been modified, by removal of the piston within the fuel reservoir, to allow the degraded fuel to return to the reservoir and mix with the fresh fuel. At the end of test the steel tube is removed and the level of deposit measured as surface carbon.
The results are shown in Table 3 below. It can be seen that in order to achieve a significant reduction in deposits, treat rates in excess of 120 ppm of additive A are needed. The reduction in deposits observed at a treat rate of 144 ppm is far in excess of the reduction that would be predicted based on the results for treat rates of 48 and 96 ppm.










TABLE 3






Fuel
A
Surface carbon



Composition
(ppm active)
(μg/cm2)



















1 (ref)
—
117



2 (comp)
48
124



3 (comp)
96
101



4 (inv)
144
49



5 (inv)
192
29









Example 3
The engine of the CEC DW 10 injector fouling test method is the PSA DW10BTED4. In summary, the engine characteristics are:
Design: Four cylinders in line, overhead camshaft, turbocharged with EGR
Capacity: 1998 cm3 
Combustion chamber: Four valves, bowl in piston, wall guided direct injection
Power: 100 kW at 4000 rpm
Torque: 320 Nm at 2000 rpm
Injection system: Common rail with piezo electronically controlled 6-hole injectors.
Max. pressure: 1600 bar (1.6×108 Pa). Proprietary design by SIEMENS VDO
Emissions control: Conforms with Euro IV limit values when combined with exhaust gas post-treatment system (DPF)
This engine was chosen as a design representative of the modern European high-speed direct injection diesel engine capable of conforming to present and future European emissions requirements. The common rail injection system uses a highly efficient nozzle design with rounded inlet edges and conical spray holes for optimal hydraulic flow. This type of nozzle, when combined with high fuel pressure has allowed advances to be achieved in combustion efficiency, reduced noise and reduced fuel consumption, but are sensitive to influences that can disturb the fuel flow, such as deposit formation in the spray holes. The presence of these deposits causes a significant loss of engine power and increased raw emissions.
The test is run with a future injector design representative of anticipated Euro V injector technology.
It is considered necessary to establish a reliable baseline of injector condition before beginning fouling tests, so a sixteen hour running-in schedule for the test injectors is specified, using non-fouling reference fuel.
Full details of the CEC F-98-08 test method can be obtained from the CEC. The coking cycle is summarised below.
1. A warm up cycle (12 minutes) according to the following regime:
















Duration
Engine Speed
Torque



Step
(minutes)
(rpm)
(Nm)




















1
2
idle
<5



2
3
2000
50



3
4
3500
75



4
3
4000
100









2. 8 hrs of engine operation consisting of 8 repeats of the following cycle:
















Duration
Engine Speed
Load
Torque
Boost Air


Step
(minutes)
(rpm)
(%)
(Nm)
After IC (° C.)




















1
2
1750
(20)
62
45


2
7
3000
(60)
173 
50


3
2
1750
(20)
62
45


4
7
3500
(80)
212 
50


5
2
1750
(20)
62
45


6
10
4000
100 
*
50


7
2
1250
(10)
20
43


8
7
3000
100 
*
50


9
2
1250
(10)
20
43


10
10
2000
100 
*
50


11
2
1250
(10)
20
43


12
7
4000
100 
*
50





* for expected range see CEC-F-98-08 method






3. Cool down to idle in 60 seconds and idle for 10 seconds
4. 8 hrs soak period
The standard CEC F-98-08 test method consists of 32 hours engine operation corresponding to 4 repeats of steps 1-3 above, and 3 repeats of step 4. ie 56 hours total test time excluding warm ups and cool downs.
Diesel fuel compositions were prepared comprising the additive and at the treat rates listed in Table 3, added to a blend of RF06 base fuel containing 10% of bio diesel in the form of Rapeseed Oil Methyl Ester conforming to EN14214 specification, and the blend tested according to the CEC DW 10 method of described above. Power losses were recorded after a period of 24 hours of engine operating time corresponding to 3 operating cycles. Results are presented in Table 4 below.










TABLE 4







A
Power Loss %



Fuel
(ppm
after 24 hrs



Composition
active)
engine operation



















6 (ref)
—
8



7 (inv)
384
4.5



8 (inv)
576
0









Example 4
Diesel fuel compositions were prepared comprising the additive and treat rate listed in Table 5, added to an RF06 base fuel containing 1 ppm zinc (as zinc neodecanoate) and tested according to the DW 10 method. Power loss was recorded after periods of 24 and 32 hours of engine operating time corresponding to 3 and 4 operating cycles.









TABLE 5








Power Loss %














A
after 24 hours
after 32 hours



Fuel
(ppm
of engine
of engine



Composition
active)
operation
operation















 9 (ref)
—
8.7
10.9



10 (ref)
96
5.3
6.6



11 (inv)
288
2.2
3.1

## Claims

1. A method for improving the performance of a diesel engine having a high pressure fuel system comprising adding 140 to 750 ppm of a nitrogen-containing detergent to diesel fuel; wherein the nitrogen-containing detergent is the reaction product of a carboxylic-derived acylating agent having a hydrocarbyl substituent of number average molecular mass of 170 to 2800 and a polyamine; and wherein the or each injector of the high pressure diesel engine has a diameter of less than 500 μm wherein the improvement in performance is measured by a reduction in power loss of the engine and/or a reduction in deposits in a vehicle fuel filter.

2. The method according to claim 1, wherein the engine has a pressure in excess of 1350 bar.

3. The method according, to claim 1, wherein the improvement in performance is measured by a reduction in deposits on the injectors of the engine.

4. The method according to claim 1, wherein the nitrogen-containing detergent is the reaction product of a substituted succinic acid derivative and a polyamine.

5. The method according to claim 4, wherein the succinic acid derivative is substituted with a polyisobutene group having a molecular weight of between 250 and 1500.

6. The method according to claim 4, wherein the succinic acid derivative is substituted with a polyisobutene group having a molecular weight of between 650 and 1200.

7. The method according to claim 1 wherein the polyamine is a polyethylene polyamine having between 3 to 9 nitrogen atoms.