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    • 专利摘要:
    COMPOSITION OF DIESEL FUEL, ADDITIVE PACKAGE, USE OF AN ADDITIVE AND USE OF A COMPOSITION OF DIESEL FUEL. The present invention relates to a diesel fuel composition comprising, as an additive, a quaternary ammonium salt formed by the reaction of a compound of formula (A): and a compound formed by the reaction of a substituted hydrocarbyl acylating agent and a amine of the formula (B1) or (B2): where R is an optionally substituted alkyl, alkenyl, aryl or alkylaryl group; R1 is a C1 to C22 alkyl, aryl or alkylaryl group; R2 and R3 are the same or different alkyl groups having from 1 to 22 carbon atoms; X is an alkylene group having from 1 to 20 carbon atoms; n is 0 to 20; m is 1 to 5; and R4 is hydrogen or a C1 to C22 alkyl group.
    公开号:BR112012018408B1
    申请号:R112012018408-3
    申请日:2011-02-04
    公开日:2020-12-29
    发明作者:Vince Burgess；Simon Mulqueen；Jacqueline Reid
    申请人:Innospec Limited；
    IPC主号:
    专利说明:

    [0001] The present invention relates to fuel compositions and additives thereof. In particular, the invention relates to additives for diesel fuel compositions, especially those suitable for use in modern diesel engines with high pressure fuel systems.
    [0002] Due to consumer demand and legislation, diesel engines, in recent years, have become much more energy efficient, have shown better performance and have had their emissions reduced.
    [0003] These improvements in performance and emissions have been brought about by improvements in the combustion process. To achieve the atomization of the fuel needed for this improved combustion, fuel injection equipment has been developed, which uses higher fuel injection pressures and reduced diameters of the injection nozzle orifice. The fuel pressure in the injection nozzle is now commonly in excess of 1500 bar (1.5 x 108Pa). 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 fuel degradation.
    [0004] Diesel engines that have a high pressure fuel system may include, but are not limited to, heavy-duty diesel engines and smaller passenger car diesel engines. Heavy diesel engines can include very powerful engines, such as the MTU 4000 series diesel having 20 alternative cylinders designed primarily for ships and power generation with power up to 4300 kW or engines, such as the Renault DXi 7 having 6 cylinders and a power around 240 kW. A typical passenger car diesel engine is the Peugeot DW10 with 4 cylinders and power of 100 kW or less, depending on the variant.
    [0005] In all diesel engines related to the present invention, a common feature is a high pressure fuel system. Typically pressures greater than 1350 bar (1.35 x 108Pa) are used, but pressures of up to 2000 bar (2 x 108Pa) or more can often exist.
    [0006] Two non-limiting examples of such high pressure fuel systems are: the common rail injection system, in which the fuel is compressed using a high pressure pump, which supplies it to the fuel injection valves via a common rail, and the unit injection system that integrates the high pressure pump and a fuel injection valve in one assembly, achieve the highest possible injection pressures exceeding 2000 bar (2 x 108Pa). In both systems, when the fuel is pressurized, the fuel gets hot, often at temperatures around 100 ° C, or above.
    [0007] In common rail systems, fuel is stored at high pressure on the central accumulator track or separate accumulators before being delivered to the injectors. Often, some heated fuel is returned to the low pressure side of the fuel system or returned to the fuel tank. In unit injection systems, fuel is compressed inside the injector in order to generate high injection pressures. This, in turn, increases the temperature of the fuel.
    [0008] In both systems, fuel is present in the injector body, prior to injection, where it is further heated due to the heat of the combustion chamber. The fuel temperature at the injector end can be as high as 250 to 350 ° C.
    [0009] Thus, the fuel is increased at pressures from 1350 bar (1.35 x 108Pa) to over 2000 bar (2 x 108Pa) and temperatures of about 100 ° C to 350 ° C before injection, sometimes being recirculated back into the fuel system, thus increasing the time for which the fuel faces these conditions.
    [0010] A common problem with diesel engines is blockage of the injector, particularly the injector body, and the injection nozzle. Obstructions can also occur in the fuel filter. Blockage of the injection nozzle occurs when the nozzle is blocked with deposits from diesel fuel. The clogging of fuel filters may be related to the recirculation of the fuel back into the fuel tank. Deposits increase with fuel degradation. The deposits can take the form of residues such as carbonaceous coke or sticky residues or as gum. Diesel fuel becomes more and more unstable the more they are heated, especially if heated under pressure. Thus, diesel engines with high pressure fuel systems can cause increased fuel degradation.
    [0011] The injector clogging problem can occur when using any type of diesel fuel. However, some fuels can be particularly prone to cause clogging or the clogging can occur more quickly when these fuels are used. For example, fuels containing biodiesel produce injector clogs more readily. Diesel fuel containing metallic species can also lead to an increase in deposits. Metallic species can be deliberately added to the fuel in additive compositions or they can be present as contaminating 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 the fuel.
    [0012] Transition metals, in particular, cause increased deposits, especially copper and zinc species. These can typically be presented in levels of a few ppb (parts per billion) up to 50 ppm, but levels that are likely to cause problems are believed to be 0.1 to 50 ppm, for example, 0.1 to 10 ppm.
    [0013] When the injectors become blocked or partially blocked, the delivery of fuel is less efficient and there is little mixing of the fuel with the air. Over time this leads to a loss of engine power, increased exhaust emissions and poor fuel economy.
    [0014] As the size of the injection nozzle orifice is reduced, the relative impact of the deposit formation becomes more significant. By simple arithmetic, a 5 μM deposit layer within a 500 μM hole reduces the flow area by 4% while the same 5 μM deposit layer in a 200 μM hole reduces the flow area by 9.8 %.
    [0015] Currently, nitrogen-containing detergents can be added to diesel fuel to reduce coke. Typical nitrogen-containing detergents are those formed by reacting a polyisobutylene succinic acid derivative substituted with a polyalkylene polyamine. However, newer engines, including thinner injection nozzles are more sensitive and the current diesel fuel may not be suitable for use with new engines that incorporate these smaller nozzle orifices.
    [0016] The present inventor has developed diesel fuel compositions, which, when used in diesel engines having a high pressure fuel system, provides improved performance compared to prior art diesel fuel compositions.
    [0017] It is advantageous to provide a diesel fuel composition which prevents or reduces the occurrence of deposits in a diesel engine. Such fuel compositions can be considered to perform a "keep clean" function, that is, they prevent or inhibit obstruction.
    [0018] However, it would also be desirable to provide a diesel fuel composition which would help to clean deposits that are already formed in an engine, in particular deposits that have been formed in the injectors. Such a composition of fuel that, when burned in a diesel engine removes deposits from there, therefore, they "clean" an already blocked engine.
    [0019] As in "keep clean" properties, the "clean-up" of a blocked engine can provide significant advantages. For example, superior cleaning can lead to an increase in power and / or an increase in fuel economy. In addition, removing deposits from an engine, especially from injectors, can lead to an increase in the time interval when maintenance or replacement of the injector is necessary, thus reducing maintenance costs.
    [0020] Although, for the reasons mentioned above, deposits on injectors is a particular problem found in modern diesel engines with high pressure fuel systems, it is desirable to provide a diesel fuel composition, which also provides effective detergency in more traditional diesel engines such that a single fuel supplied at the pumps can be used in engines of all types.
    [0021] It is also desirable that the fuel compositions reduce the clogging of the vehicle's fuel filters. It would be useful to provide compositions that prevent or inhibit the occurrence of fuel filter deposits, that is, they provide a "keep clean" function. It would be useful to provide compositions that remove existing deposits from fuel filter deposits, that is, to provide a “clean up” function. Compositions capable of providing these two functions would be especially useful.
    [0022] In accordance with a first aspect of the present invention, a diesel fuel composition is provided comprising, as an additive, a quaternary ammonium salt formed by the reaction of a compound of formula (A):
    and a compound formed by the reaction of a substituted hydrocarbyl acylating agent and an amine of the formula (B1) or (B2):

    [0023] Where R is an optionally substituted alkyl, alkene, aryl or alkylaryl group; R1 is a C1 to C22 alkyl, aryl or alkylaryl group; R2 and R3 are the same groups or different alkyls having 1 to 22 carbon atoms, X is an alkylene group having 1 to 20 carbon atoms; n is 0 to 20; m is 1 to 5; and R4 is hydrogen or a C1 to C22 alkyl group.
    [0024] These additive compounds can be referred to here as "the quaternary ammonium salt additives".
    [0025] The compound of formula (A) is an ester of a carboxylic acid capable of reacting with a tertiary amine to form an ammonium salt quaternary ammonium salt.
    [0026] Appropriate compounds of formula (A) include esters of carboxylic acids having a pKa of 3.5 or less.
    [0027] The compound of formula (A) is preferably an ester of a carboxylic acid selected from a substituted aromatic carboxylic acid, a-hydroxycarboxylic acid and a polycarboxylic acid.
    [0028] In some preferred embodiments, the compound of formula (A) is an ester of a substituted aromatic carboxylic acid, and thus R is a substituted aryl group.
    [0029] Preferably R is a substituted aryl group having 6 to 10 carbon atoms, preferably a phenyl or naphthyl group, more preferably a phenyl group. R is suitably substituted with one or more groups selected from carboalkoxy, nitro, cyano, hydroxy, SR5 or NR5R6. Each of R5 and R6 may be hydrogen or optionally substituted alkyl groups, alkene, aryl or carboalkoxy. Preferably, each of R5 and R6 is hydrogen or an optionally substituted C1 to C22 alkyl group, preferably hydrogen or a C1 to C16 alkyl group, preferably hydrogen or a C1 to C10 alkyl group, more preferably C1 to C4 alkyl group. Preferably, R5 is hydrogen and R6 is hydrogen or a C1 to C4 alkyl group. More preferably R5 and R6 are both hydrogen. Preferably R is an aryl group substituted with one or more groups selected from hydroxyl, carboalkoxy, nitro, cyano and NH2. R can be a polysubstituted aryl group, for example, trihydroxyphenyl. Preferably R is a monosubstituted aryl group. Preferably R is an ortho-substituted aryl group. Suitably R is substituted with a group selected from OH, NH2, NO2 or COOMe. Preferably R is substituted with an OH or NH2 group. Suitably R is a substituted aryl hydroxy group. More preferably R is a 2-hydroxyphenyl group.
    [0030] Preferably, R1 is an alkyl or alkylaryl group. R1 may be a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group, suitably a C1 to C8 alkyl group. R1 may be a C1 to C16 alkylaryl group, preferably a C1 to C10 alkyl group, suitably a C1 to C8 alkylaryl group. R1 can be methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer. Preferably, R1 is benzyl or methyl. Most preferably R1 is methyl.
    [0031] An especially preferred compound of formula (A) is methyl salicylate.
    [0032] In some embodiments, the compound of formula (A) is an ester of a-hydroxycarboxylic acid. In such modalities the compound of formula (A) has the structure:
    wherein R7 and R8 are the same or different and each is selected from hydrogen, alkyl, alkene, aralkyl or aryl. Such compounds suitable for use here are described in EP 1254889.
    [0033] Examples of compounds of the formula (A) in which RCOO is the residue of an α-hydroxycarboxylic acid include esters of methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and 2-hydroxy-isobutyric acid allyl; methyl-, ethyl-, propyl, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxy-2-methylbutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxy-2-ethylbutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of lactic acid, and methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, allyl, benzyl-, and glycolic acid phenyl. The foregoing, a preferred compound is methyl 2-hydroxy-isobutyrate.
    [0034] In some embodiments, the compound of formula (A) is an ester of a polycarboxylic acid. This definition is intended to include dicarboxylic acids and carboxylic acids having more than 2 portions of acids. In such embodiments RCOO is preferably present in the form of an ester, that is, one or more additional acid groups present in the group R are in esterified form. Preferred esters are C1 to C4 alkyl esters.
    [0035] Compound (A) can be selected from oxalic acid diester, phthalic acid diester, maleic acid diester, malonic acid diester or citric acid diester. An especially preferred compound of the formula (A) is dimethyl oxalate.
    [0036] In preferred embodiments the compound of formula (A) is an ester of a carboxylic acid having a pKa of less than 3.5. In such modalities in which the compound includes more than one acid group, we intend to refer to the first dissociation constant.
    [0037] Compound (A) can be selected from an ester of a carboxylic acid selected from one or more oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2,4,6-trihydrobenzoic acid.
    [0038] Preferred compounds of formula (A) include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.
    [0039] To form the quaternary ammonium salt additives of the present invention the compound of formula (A) is reacted with a compound formed by the reaction of a substituted hydrocarbyl acylating agent and an amine of formula (B1) or (B2).
    [0040] When a compound of the formula (B1) is used, R4 is preferably hydrogen or a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group, more preferably a C1 to C6 alkyl group. Most preferably R4 is selected from hydrogen, methyl, ethyl, propyl, butyl and their isomers. Most preferably R4 is hydrogen.
    [0041] When a compound of the formula (B2) is used, m is preferably 2 or 3, more preferably 2; n is preferably 0 to 15, preferably 0 to 10, more preferably 0 to 5. More preferably n is 0 and the compound of formula (B2) is an alcohol.
    [0042] Preferably, the substituted hydrocarbyl acylating agent reacts with a diamine compound of formula (B1).
    [0043] R2 and R3 can each be, independently, a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group. R2 and R3 may independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or an isomer of any of these. Preferably, R2 and R3, each independently, is C1 to C4 alkyl. Preferably, R2 is methyl. Preferably, R3 is methyl.
    [0044] X is preferably an alkylene group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example, 2 to 6 carbon atoms or 2 to 5 carbon atoms. More preferably X is an ethylene, propylene or butylene group, especially a propylene group.
    [0045] An especially preferred compound of the formula (B1) is dimethylaminopropylamine.
    [0046] The amine of the formula (B1) or (B2) reacts with a substituted hydrocarbyl acylating agent. The substituted hydrocarbyl acylating agent can be based on a substituted mono- or polycarboxylic hydrocarbyl acid or a reactive equivalent thereof. Preferably, the substituted hydrocarbyl acylating agent is a hydrocarbyl composed of substituted succinic acid such as succinic acid or succinic anhydride.
    [0047] The substituted hydrocarbyl preferably comprises at least 10, more preferably at least 12, for example, 30 or 50 carbon atoms. It can comprise up to about 200 carbon atoms. Preferably the substituted hydrocarbyl has a numerical average molecular weight (Mn) between 170 to 2800, for example, from 250 to 1500, preferably from 500 to 1500 and more preferably from 500 to 1100. An Mn of 700 to 1300 is especially preferred.
    [0048] The hydrocarbyl base substituents can be made from homo- or interpolymers (for example, copolymers, terpolymers) of mono- and diolefins with 2 to 10 carbon atoms, for example, ethylene, propylene, butane-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. Preferably these olefins are 1-mono-olefins. The substituted hydrocarbyl can also be derived from the halogenated analogs (e.g., chlorinated or brominated) of such homo- or interpolymers. Alternatively, the substituent can be made from other sources, for example, high monomeric molecular weight alkenes (for example, 1-tetra-contene) and chlorinated analogues and hydrochlorinated analogues thereof, aliphatic oil fractions, for example, waxes paraffin and crackers and chlorinated analogues and hydrochlorinated analogues thereof, white oils, synthetic alkenes, for example, produced by the Ziegler-Natta process (for example, poly (ethylene) greases) and other sources known to those skilled in the art. Any unsaturation in the substituent can, if desired, be reduced or eliminated by hydrogenation according to procedures known in the art.
    [0049] The term "hydrocarbyl" as used herein denotes a group having a carbon atom attached directly to the rest of the molecule, and having a predominantly aliphatic hydrocarbon character. Suitable hydrocarbyl base groups can contain non-hydrocarbon moieties. For example, they may contain up to one non-hydrocarbyl group for every ten carbon atoms provided that 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, oxygen, halo (especially chlorine and fluorine), alkoxyl, mercapto alkyl, alkyl sulfoxy, etc. Preferred hydrocarbyl base substituents are purely aliphatic hydrocarbons in nature and do not contain such groups.
    [0050] The hydrocarbyl base substituents are preferably predominantly saturated, that is, they contain no more than one unsaturated carbon-carbon bond for every ten simple carbon-carbon bonds present. Most preferably they contain no more than one unsaturated carbon-carbon bond for every 50 carbon-carbon bonds present.
    [0051] Preferred hydrocarbyl base substituents are poly (isobutenes) known in the art. Thus, in especially preferred embodiments, the substituted hydrocarbyl acylating agent is a substituted polyisobutenyl succinic anhydride.
    [0052] The preparation of substituted polyisobutenyl succinic anhydride (PIBSA) is documented in the art. Suitable processes include thermal reactions of polyisobutenes with maleic anhydride (see, for example, US-A-3,361,673 and US-A-3,018,250), and reacting a halogenate, in particular a polyisobutene chloride, (PIB) with anhydride maleic (see, for example, US-A-3,172,892). Alternatively, the polyisobutenyl succinic anhydride can be prepared by mixing polyolefin with maleic anhydride and passing chlorine through the mixture (see, for example, GB-A-949,981).
    [0053] 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 in which 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 that have more than 80 mol% and up to 100% terminal vinylidene groups such as those described in EP1344785.
    [0054] Other preferred hydrocarbyl groups include those having an internal olefin, for example, as described in applicant's published patent application WO2007 / 015080.
    [0055] An internal olefin as used hereinafter means any olefin predominantly containing a non-alpha double bond, which is a beta or higher olefin. Preferably such materials are substantially and completely beta-olefins or higher, for example, containing less than 10% by weight of alpha olefin, more preferably less than 5% by weight or less than 2% by weight. Typical internal olephins include Neodeno 1518IO available from Shell.
    [0056] Internal olefins are sometimes like isomerized olefins and can be prepared from alpha olefins by an isomerization process known in the art, or are available from other sources. The fact that they are also known as internal olefins reflects that they do not necessarily have to be prepared by isomerization.
    [0057] In especially preferred embodiments, the quaternary ammonium salt additives of the present invention are tertiary amine salts prepared from dimethylamino propylamine and a polyisobutylene-substituted succinic anhydride. The average molecular weight of the polyisobutylene substituent is preferably 700 to 1300.
    [0058] The quaternary ammonium salt additives of the present invention can be prepared by any suitable methods. Such methods will be known to the person skilled in the art and are exemplified here. Typically, quaternary ammonium salt additives will be prepared by heating a compound of formula (A) and a compound of formula (B1) or (B2) in a molar ratio of approximately 1: 1, optionally in the presence of a solvent. The resulting crude reaction mixture can be added directly to a diesel fuel, optionally following the removal of the solvent. It was found that no residual by-product or starting material still present in the mixture causes any damage to the performance of the additive. Thus, the present invention can provide a diesel fuel composition comprising the reaction product of a compound of formula (A) and a compound of formula (B1) or (B2).
    [0059] In some embodiments, the composition of the present invention may comprise an additional additive, this additional additive being the product of a Mannich reaction between: (a) an aldehyde; (b) a polyamine; and (c) an optionally substituted phenol.
    [0060] These compounds can then be designated as "Mannich's additives". Thus in some preferred embodiments, the present invention provides a diesel fuel composition comprising a quaternary ammonium salt additive and a Mannich additive.
    [0061] Any aldehyde can be used as an aldehyde component (a) of the Mannich additive. Preferably, the aldehyde component (a) is an aliphatic aldehyde. Preferably, the aldehyde has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Most preferably, the aldehyde is formaldehyde.
    [0062] The polyamine component (b) of the Mannich additive can be selected from any compound including two or more amine groups. Preferably, the polyamine is a polyalkylene polyamine. Preferably, the polyamine is a polyalkylene polyamine in which the alkylene component has 1 to 6, preferably 1 to 4, more preferably 2 to 3 carbon atoms. More preferably, the polyamine is a polyethylene polyamine.
    [0063] Preferably, the polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.
    Preferably, the polyamine component (b) includes the R1R2NCHR3CHR4NR5R6 portion in which each of R1, R2R3, R4, R5 and R6 is independently selected from hydrogen, and an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl substituent.
    Thus, the polyamine reagents used to make the Mannich reaction products of the present invention preferably include an optionally substituted ethylene diamine residue.
    [0066] Preferably, at least one of R1 and R2 is hydrogen. Preferably, both of R1 and R2 are hydrogen.
    [0067] Preferably, at least two of R1, R2, R5 and R6 are hydrogen.
    [0068] Preferably, at least one of R3 and R4 is hydrogen. In some preferred embodiments, each of R3 and R4 is hydrogen. In some embodiments, R3 is hydrogen and R4 is alkyl, for example, C1 to C4 alkyl, especially methyl.
    [0069] Preferably, at least one of R5 and R6 is an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl substituent.
    [0070] In modalities in which at least one of R1, R2, R3, R4, R5 and R6 is not hydrogen, each is independently selected from an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl moiety. Preferably, each is independently selected from hydrogen and an optionally substituted C (1-6) alkyl moiety.
    [0071] In particularly preferred compounds, each of R1, R2, R3, R4 and R5 is hydrogen and R6 is an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl substituent. Preferably, R6 is an optionally substituted C (1-6) alkyl moiety.
    [0072] Such an alkyl moiety may be substituted with one or more selected groups of hydroxyl, amino (especially unsubstituted amino; -NH-, - NH2), sulfo, sulfoxy, C (1-4) alkoxy, nitro, halo (especially chlorine or fluorine) and mercapto.
    [0073] There may be one or more heteroatoms incorporated within the alkyl chain, for example, O, N or S, to provide an ether, amine or thioether.
    [0074] Especially preferred substituents R1, R2, R3, R4, R5or R6 are hydroxy-C (1-4) alkyl and amino-C (1-4) alkyl, especially HO-CH2-CH2- and H2N-CH2-CH2 -.
    [0075] Suitably, the polyamine includes only the amine functionality, or the amine and alcohol functionalities.
    [0076] The polyamine can, for example, be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenopentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethylene-octamine, propane-1,2-diamine, 2 (2-amino-ethylamine) ethanol, and , N'-bis (2-aminoethyl) ethylenediamine (N (CH2CH2NH2) 3). More preferably, the polyamine comprises tetraethylenepentamine or ethylenediamine.
    [0077] Commercially available polyamine sources typically contain mixtures of isomers and / or oligomers, and products prepared from these commercially available mixtures are within the scope of the present invention.
    [0078] The polyamines used to form the Mannich additives of the present invention can be straight or branched, and can include cyclic structures.
    [0079] In the preferred embodiments, the Mannich additives of the present invention are of relatively low molecular weight.
    Preferably, Mannich's additive product molecules have a numerical average molecular weight of less than 10,000, preferably less than 7500, preferably less than 2000, more preferably less than 1500.
    [0081] The optionally substituted phenol component (c) can be substituted with 0 to 4 groups on the aromatic ring (in addition to the phenol OH). For example, it can be a tri- or disubstituted phenol. More preferably, component (c) is a monosubstituted phenol. The substitution may be in the ortho, and / or goal, and / or para position (s).
    [0082] Each phenol portion can be ortho, meta or to be replaced with the aldehyde / amine residue. The compounds in which the aldehyde residue is ortho or substituted are most commonly formed. Mixtures of the compounds can result. In the preferred embodiments, the starting phenol is to be substituted and, thus, the ortho substituted product results.
    [0083] Phenol can be substituted with any common group, for example, one or more among an alkyl group, an alkenyl group, an alkynyl group, a nitrile group, a carboxylic acid, an ester, an ether, an alkoxy group, a halo group, an additional hydroxyl group, a mercapto group, an alkyl mercapto group, an alkyl sulfoxy group, a sulfoxy group, an aryl group, an arylalkyl group, a substituted or unsubstituted amino group or a nitro group.
    [0084] Preferably, the phenol carries one or more optionally substituted alkyl substituents. The alkyl substituent can be optionally substituted with, for example, hydroxyl, halo, (especially chlorine and fluorine), alkoxy, alkyl, mercapto, alkyl sulfoxy, aryl or amino residues. Preferably, the alkyl group consists essentially of carbon and hydrogen atoms. The substituted phenol can include an alkenyl or alkynyl residue including one or more double and / or triple bonds. More preferably, component (c) is an alkyl-substituted phenol group in which the alkyl chain is saturated. The alkyl chain can be straight or branched.
    [0085] Preferably, component (c) is a monoalkyl phenol, especially a para-substituted monoalkyl phenol.
    [0086] Preferably, component (c) comprises a substituted alkyl phenol in which the phenol carries one or more alkyl chains having a total of less than 28 carbon atoms, preferably less than 24 carbon atoms, more preferably less than 20 carbon atoms, preferably less than 18 carbon atoms, preferably less than 16 carbon atoms and more preferably less than 14 carbon atoms.
    [0087] Preferably, the or each alkyl substituent of component (c) has 4 to 20 carbon atoms, preferably 6 to 18, more preferably 8 to 16, especially 10 to 14 carbon atoms. In a particularly preferred embodiment, component (c) is a phenol having a C12 alkyl substituent.
    [0088] Preferably, the or each phenol component substituent (c) has a molecular weight of less than 400, preferably less than 350, preferably less than 300, more preferably less than 250 and more preferably less than 200 The or each substituent of the phenol component (c) may suitably have a molecular weight of 100 to 250, for example, 150 to 200.
    [0089] Molecules of component (c) preferably have an average molecular weight of less than 1800, preferably less than 800, preferably less than 500, more preferably less than 450, preferably less than 400, preferably less than than 350, more preferably less than 325, preferably less than 300 and more preferably less than 275.
    [0090] Components (a), (b) and (c) can each comprise a mixture of compounds and / or a mixture of isomers.
    [0091] Mannich's additive is preferably the reaction product obtained by reaction components (a), (b) and (c) in a molar ratio of 5: 1: 5 to 0.1: 1: 0.1, more preferably from 3: 1: 3 to 0.5: 1: 0.5.
    [0092] To form the Mannich additive of the present invention, components (a) and (b) are preferably reacted in a molar ratio of 6: 1 to 1: 4 (aldehyde: polyamine), preferably from 4: 1 to 1 : 2, more preferably from 3: 1 to 1: 1.
    [0093] To form a preferred Mannich additive of the present invention, the molar ratio of component (a) to component (c) (aldehyde: phenol) in the reaction mixture is preferably 5: 1 to 1: 4, preferably 3 : 1 to 1: 2, for example, from 1.5: 1 to 1: 1.1.
    [0094] Some preferred compounds used in the present invention are typically formed by reaction components (a), (b) and (c) in a molar ratio of 2 parts (A) to 1 part (b) ± 0.2 part ( b), for 2 parts (c) ± 0.4 part (c); preferably approximately 2: 1: 2 (a: b: c).
    [0095] Some preferred compounds used in the present invention are typically formed by the reaction components (a), (b) and (c) in a molar ratio of 2 parts (A) to 1 part (b) ± 0.2 part ( b), for 1.5 part (c) ± 0.3 part (c); preferably approximately 2: 1: 1.5 (a: b: c).
    [0096] Adequate treatment rates for the quaternary ammonium salt additive and, when present, Mannich's additive will depend on the desired performance and the type of engine in which they are used. For example, different levels of additive may be required to achieve different levels of performance.
    [0097] Suitably, the quaternary ammonium salt additive is present in the diesel fuel composition in an amount of less than 10000ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 250 ppm.
    [0098] Suitably, the Mannich additive when used is present in the diesel fuel composition in an amount of less than 10,000 ppm, 1000ppm preferably less than 500 ppm, preferably less than 250 ppm.
    [0099] The weight ratio of the quaternary ammonium salt additive to the Mannich additive is preferably from 1:10 to 10: 1, preferably from 1: 4 to 4: 1.
    [00100] As previously indicated, fuels containing biodiesel or metals are known to cause fouling. Strong fuels, for example, those containing high levels of metals and / or high levels of biodiesel may require higher treatment rates for the quaternary ammonium salt additive and / or Mannich additive than fuels that are less strong.
    [00101] The diesel fuel composition of the present invention can include one or more additional additives such as those that are commonly found in diesel fuels. These include, for example, antioxidants, dispersants, detergents, metal deactivating compounds, anti-sedimentation wax agents, cold flow improvers, cetane improvers, mist eliminators, stabilizers, demulsifiers, defoamers, corrosion inhibitors, lubricity enhancers, dyes, markers, combustion improvers, metal deactivators, odor masks, resistance reducers and conductivity improvers. Examples of suitable amounts of each of these types of additives will be known to the person skilled in the art.
    [00102] In some preferred embodiments, the composition comprises a detergent of the type formed by the reaction of a polyisobutene-substituted acylating agent derived from succinic acid and a polyethylene polyamine. Suitable compounds are, for example, described in WO2009 / 040583.
    [00103] Diesel fuel means any fuel suitable for use in a diesel engine, whether for use on the road or for use off the road. This includes, but is not limited to, fuels described as diesel, marine diesel, heavy fuel oil, industrial fuel oil, etc.
    [00104] The diesel fuel composition of the present invention can comprise a petroleum-based fuel oil, especially a medium distilled fuel oil. Such distillate fuel oils generally boil within the range of 110 ° C to 500 ° C, for example, 150 ° C to 400 ° C. Diesel fuel can comprise atmospheric distillate or vacuum distillate, cracked diesel fuel, or a mixture in any proportion of refinery flows and straight path such as thermally and / or catalytically cracked and hydrocracked distillates.
    [00105] The diesel fuel composition of the present invention can comprise non-renewable Fischer-Tropsch fuels such as those described as GTL fuels (gas-to-liquid), CTL fuels (coal-to-liquid) and OTL fuels (oil sands- para-liquid).
    [00106] The diesel fuel composition of the present invention can comprise a renewable fuel such as a biofuel composition or biodiesel composition.
    [00107] The composition of diesel fuel can comprise a first generation biodiesel. First generation biodiesel contains esters of, for example, vegetable oils, animal fats and fats used for cooking. This form of biodiesel can be obtained by transesterifying oils, for example, rapeseed oil, soybean oil, safflower oil, castor oil, corn oil, peanut oil, cottonseed oil, tallow oil, oil coconut oil, pine nut oil (Jatropha), sunflower oil, oils used for cooking, hydrogenated vegetable oils or any mixture thereof, with an alcohol, usually a mono-alcohol, in the presence of a catalyst.
    [00108] The composition of diesel fuel can comprise second generation biodiesel. Second generation biodiesel is derived from renewable resources such as vegetable oils and animal fats and processed, often at the refinery, often using hydroprocessing such as the H-Bio process developed by Petrobras. Second-generation biodiesel can be similar in properties and quality to petroleum-based fuel oil flows, for example, renewed diesel produced from vegetable oils, animal fats, etc. and marketed by ConocoPhillips as Renewable Diesel and by Neste as NExBTL.
    [00109] The diesel fuel composition of the present invention can comprise third generation biodiesel. Third generation biodiesel uses 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 entire plant (biomass) and thus increases the base of the raw material.
    [00110] The diesel fuel composition may contain mixtures of any or all of the diesel fuel compositions above.
    [00111] In some embodiments, the diesel fuel composition of the present invention can be a blended diesel fuel comprising biodiesel. In such mixtures, biodiesel can 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%.
    [00112] In some embodiments, the composition of diesel fuel may comprise a secondary fuel, for example, ethanol. Preferably, however, the diesel fuel composition does not contain ethanol.
    [00113] The diesel fuel composition of the present invention can contain a relatively high sulfur content, for example, greater than 0.05% by weight, such as 0.1% or 0.2%.
    [00114] However, in the preferred embodiments, diesel fuel has a sulfur content of at most 0.05% by weight, more preferably at most 0.035% by weight, especially at most 0.015%. Fuels with even lower levels of sulfur are also suitable such as fuels with less than 50 ppm sulfur by weight, preferably less than 20 ppm, for example, 10 ppm or less.
    [00115] Commonly when present, species containing metal will be present as a contaminant, for example, through the corrosion of the metal and metal oxide surfaces by acidic species present in the fuel or lubricating oil. In use, fuels such as diesel fuels routinely come into contact with metal surfaces, for example, in vehicle fueling systems, fuel tanks, means of transporting fuel, etc. Typically, metal-containing contamination may comprise transition metals such as zinc, iron and copper; group I or group II metals such as sodium; and other metals such as lead.
    [00116] In addition to metal-containing contamination, which may be present in diesel fuels, there are circumstances where metal-containing species may be deliberately added to the fuel. For example, as is known in the art, catalyst species carried by the fuel containing metal can be added to aid in the regeneration of particulate filters. Such catalysts are often based on metals such as iron, cerium, Group I and Group II metals, for example, calcium and strontium, either as mixtures or alone. Platinum and manganese are also used. The presence of such catalysts can also cause injector deposits when fuels are used in diesel engines having high pressure fuel systems.
    [00117] The contamination containing metal, depending on its source, can be in the form of insoluble particles or soluble compounds or complexes. Fuel-laden catalysts containing metal are often soluble compounds or complexes or colloidal species.
    [00118] In some embodiments, the metal-containing species comprise a fuel-charged catalyst.
    [00119] In some embodiments, metal-containing species comprise zinc.
    [00120] Typically, the number of species containing metal 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.
    [00121] The fuel compositions of the present invention show improved performance when used in diesel engines having high pressure fuel systems compared to prior art diesel fuels.
    [00122] According to a second aspect of the present invention, an additive package is provided which, upon addition to a diesel fuel, provides a composition of the first aspect.
    [00123] The additive package may comprise a mixture of the quaternary ammonium salt additive, Mannich's additive and optionally additional additives, for example, those described above. Alternatively, the additive package may comprise an additive solution, suitably in a mixture of hydrocarbon solvents, for example, aliphatic and / or aromatic solvents; and / or oxygenated solvents, for example, alcohols and / or ethers.
    [00124] According to a third aspect of the present invention, there is provided a method of operating a diesel engine, the method comprising combustion in the engine of a composition of the first aspect.
    [00125] According to a fourth aspect of the present invention, the use of a quaternary ammonium salt additive in a diesel fuel composition is provided to improve the performance of a diesel engine engine when using said diesel fuel composition , in which the quaternary ammonium salt is formed by the reaction of a compound of the formula (A):
    and a compound formed by the reaction of a substituted hydrocarbyl acylating agent and an amine of the formula (B1) or (B2):

    [00126] where R is an optionally substituted alkyl, alkenyl, aryl or alkylaryl group; R1 is a C1 to C22 alkyl, aryl or alkylaryl group; R2 and R3 are the same or different alkyl groups having from 1 to 22 carbon atoms; X is an alkylene group having from 1 to 20 carbon atoms; n is 0 to 20; m is 1 to 5; and R4 is hydrogen or a C1 to C22 alkyl group.
    [00127] The preferred characteristics of the second, third and fourth aspects are as defined in relation to the first aspect.
    [00128] In some especially preferred embodiments, the present invention provides the use of the combination of a quaternary ammonium salt additive and a Mannich additive as defined here to improve the performance of a diesel engine engine when using said engine composition. diesel fuel.
    [00129] The improvement in performance can be achieved by reducing or preventing the formation of deposits in a diesel engine. This can be considered an improvement in “keep clean” performance. Thus, the present invention can provide a method of reducing or preventing the formation of deposits in a diesel engine by combustion in said engine of a composition of the first aspect.
    [00130] The improvement in performance can be achieved by removing existing deposits in a diesel engine. This can be seen as an improvement in “clean up” performance. Thus, the present invention can provide a method of removing deposits from a diesel engine by combustion in said engine of a composition of the first aspect.
    [00131] In especially preferred embodiments, the composition of the first aspect of the present invention can be used to provide an improvement in "keep clean" and "clean up" performance.
    [00132] In some preferred embodiments, the use of the third aspect may relate to the use of a quaternary ammonium salt additive, optionally in combination with a Mannich additive, in a diesel fuel composition to improve the performance of a diesel engine. diesel engine when using said diesel fuel composition in which the diesel engine has a high pressure fuel system.
    [00133] Modern diesel engines having a high pressure fuel system can be characterized in several ways. Such engines are typically equipped with fuel injectors having a plurality of openings, each opening having an inlet and an outlet.
    [00134] Such modern diesel engines can be characterized by openings that are tapered such that the diameter of the inlet of the sprayer holes is larger than the diameter of the outlet.
    [00135] Such modern diesel engines can be characterized by openings having an outlet diameter of less than 500μm, preferably less than 200μm, more preferably less than 150μm, preferably less than 100μm, more preferably less than 80μm or any less.
    [00136] Such modern diesel engines can be characterized by openings where an inner edge of the entrance is rounded.
    [00137] Such modern diesel engines can be characterized by the injector having more than one opening, suitably more than 2 openings, preferably more than 4 openings, for example 6 or more openings.
    [00138] Such modern diesel engines can be characterized by a peak operating temperature in excess of 250 ° C.
    [00139] Such modern diesel engines can be characterized by a fuel pressure of more than 1.35 x 108Pa (1350 bar), preferably more than 1.5 x 108Pa (1500 bar), more preferably more than 2 x 108Pa (2000 bar).
    [00140] The use of the present invention preferably improves the performance of an engine having one or more of the characteristics described above.
    [00141] The present invention is particularly useful in preventing or reducing or removing deposits in engine injectors that operate at high pressures and temperatures in which the fuel can be recirculated and that comprise a plurality of fine openings through which the fuel is distributed for the engine. The present invention finds utility in engines for heavy vehicles and passenger vehicles. Passenger vehicles that incorporate a high-speed direct injection engine (or HSDI) can, for example, benefit from the present invention.
    [00142] Inside the injector body of modern diesel engines having a high pressure fuel system, spaces of only 1-2 μm can exist between the moving parts and there have been reports of engine problems in the field caused by locking the injectors and particularly locking the injectors open. Deposit control in this area can be very important.
    [00143] The diesel fuel compositions of the present invention can also provide improved performance when used with traditional diesel engines. Preferably, improved performance is achieved by using diesel fuel compositions in modern diesel engines having high pressure fuel systems and by using the compositions in traditional diesel engines. This is important because it allows a single fuel to be provided which can be used in new engines and old vehicles.
    [00144] The improvement in the performance of the diesel engine system can be measured in several ways. Appropriate methods will depend on the type of engine and whether “keep clean” and / or “clean up” performance is measured.
    [00145] One of the ways in which performance improvement can be measured is by measuring the loss of strength in a controlled engine test. An improvement in “keep clean” performance can be measured by observing a reduction in the loss of strength compared to that seen in a base fuel. The clean up performance can be seen by an increase in strength when the diesel fuel compositions of the invention are used in an already blocked engine.
    [00146] The improvement in the performance of the diesel engine having a high pressure fuel system can be measured by an improvement in fuel economy.
    [00147] The use of the third aspect can also improve the performance of the engine by reducing, preventing or removing deposits in the vehicle's fuel filter.
    [00148] The level of deposits in a vehicle's fuel filter can be measured quantitatively or qualitatively. In some cases, this can only be determined by inspecting the filter once the filter has been removed. In other cases, the level of deposits can be estimated during use.
    [00149] Many vehicles are fitted with a fuel filter which can be visually inspected during use to determine the level of build-up of solids and the need to replace the filter. For example, such a system uses a tube filter inside a transparent housing allowing the filter, the level of fuel inside the filter and the degree of blockage of the filter to be observed.
    [00150] The use of the fuel compositions of the present invention can result in levels of deposits on the fuel filter which are considerably reduced compared to fuel compositions not of the present invention. This allows the filter to be changed much less frequently and can ensure that the fuel filters do not fail between service intervals. Thus, the use of the compositions of the present invention can lead to reduced maintenance costs.
    [00151] In some embodiments, the occurrence of deposits on a fuel filter can be inhibited or reduced. Thus, a “keep clean” performance can be observed. In some embodiments, existing tanks can be removed from a fuel filter. Thus, a “clean up” performance can be observed.
    [00152] The improvement in performance can also be evaluated considering the extent to which the use of the fuel compositions of the invention reduces the amount of deposit in the injector of an engine. For the “keep clean” performance, a reduction in the occurrence of deposits would be observed. For “clean up” performance, the removal of existing deposits would be observed.
    [00153] Direct measurement of deposit accumulation is not generally undertaken, but is generally inferred from loss of strength or fuel flow rates through the injector.
    [00154] The use of the third aspect can improve the performance of the engine by reducing, preventing or removing deposits including gums and lacquers within the injector body.
    [00155] In Europe, the Co-ordinating European Council (European Coordination Council) for the development of performance tests for the transportation of fuels, lubricants and other fluids (the industrial body known as CEC), has developed a new test, called CEC F-98-08, to assess whether diesel fuel is suitable for use in engines meeting the new European Union emission regulations known as the “Euro 5” regulations. The test is based on a Peugeot DW10 engine using Euro 5 injectors, and will be designed below as the DW10 test. It will also be described in the context of the examples (see example 6).
    [00156] Preferably, the use of the fuel composition of the present invention leads to reduced deposits in the DW10 test. For the “keep clean” performance, a reduction in the occurrence of deposits is preferably observed. For “clean up” performance, deposit removal is preferably observed. The DW10 test is used to measure the loss of power in modern diesel engines having a high pressure fuel system.
    [00157] For older engines, an improvement in performance can be measured using the XUD9 test. This test is described in relation to example 7.
    [00158] Suitably, the use of a fuel composition of the present invention can provide "keep clean" performance in modern diesel engines, that is, the formation of deposits in the injectors of these engines can be inhibited or prevented. Preferably, this performance is such that a loss of strength of less than 5%, preferably less than 2% is observed after 32 hours as measured by the DW10 test.
    [00159] Suitably, the use of a fuel composition of the present invention can provide a "clean up" performance in modern diesel engines, that is, deposits in the injectors of an already encrusted engine can be removed. Preferably, this performance is such that the strength of an inlaid engine can be returned to within 1% of the level achieved when using clean injectors within 8 hours as measured in the DW10 test.
    [00160] Preferably, quick clean-up can be achieved in which strength is returned to within 1% of the observed level using clean injectors within 4 hours, preferably within 2 hours.
    [00161] Clean injectors may include new injectors or injectors which have been removed and physically cleaned, for example, in an ultrasound bath.
    [00162] Such performance is exemplified in example 6 and shown in figures 1 and 2.
    [00163] Suitably, the use of a fuel composition of the present invention can provide a "keep clean" performance in traditional diesel engines, that is, the formation of deposits in the injectors of these engines can be inhibited or prevented. Preferably, this performance is such that a loss of flow of less than 50%, preferably less than 30% is observed after 10 hours as measured by the XUD-9 test.
    [00164] Suitably, the use of a fuel composition of the present invention can provide a "clean up" performance on traditional diesel engines, that is, deposits on the injectors of an already encrusted engine can be removed. Preferably, this performance is such that the flow loss of an inlaid motor can be increased by 10% or more within 10 hours as measured in the XUD-9 test.
    [00165] Any feature of any aspect of the invention can be combined with any other feature, where appropriate.
    [00166] The invention will now be further defined with reference to the following non-limiting examples. In the examples that follow the values given in parts per million (ppm) to treat the rates denote the amount of active agent, not the amount of a formulation as added, and containing an active agent. All parts per million are by weight. Example 1
    [00167] Additive A, the reaction product of a substituted hydrocarbyl acylating agent and a compound of the formula (B1) was prepared as follows:
    [00168] 523.88g (0.425 moles) of PIBSA (made of 1000 MW PIB and maleic anhydride) and 373.02g of Caromax 20 were loaded into a 1 liter vessel. The mixtures were stirred and heated, under nitrogen to 50 ° C. 43.69g (0.425 moles) of dimethylaminopropylamine were added and the mixture heated to 160 ° C for 5 hours, with concurrent removal of water using a Dean-Stark device. Example 2
    [00169] Additive B, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00170] 588.24g (0.266 moles) of Additive A mixed with 40.66g (0.266 moles) of methyl salicylate under nitrogen. The mixture was stirred and heated to 160 ° C for 16 hours. The product contained 37.4% solvent. The non-volatile material contained 18% of the quaternary ammonium salt as determined by titration. Example 3
    [00171] Additive C, a Mannich additive was prepared as follows:
    [00172] A 1 liter reactor was loaded with dodecylphenol (524.6g, 2.00 moles), ethylenediamine (60.6g, 1.01 moles) and Caromax 20 (250.1g). The mixture was heated to 95 ° C and 37% by weight formaldehyde solution (167.1g, 2.06 moles), charged for 1 hour. The temperature was raised to 125 ° C for 3 hours and 125.6 g of water was removed. In this example, the molar ratio of aldehyde (a): amine (b): phenol (c) was approximately 2: 1: 2. Example 4
    [00173] Additive D, a Mannich additive was prepared as follows:
    [00174] A reactor was loaded with dodecylphenol (277.5 kg, 106 kmoles), ethylenediamine (43.8 kg, 0.73 kmoles) and Caromax 20 (196.4 kg). The mixture was heated to 95 ° C and formaldehyde solution, 36.6% by weight (119.7 kg, 1.46 kmoles), charged for 1 hour. The temperature was raised to 125 ° C for 3 hours and the water removed. In this example, the molar ratio of aldehyde (a): amine (b): phenol (c) was approximately 2: 1: 1.5. Example 5
    [00175] Diesel fuel compositions were prepared comprising the additives listed in table 1, added to aliquots all taken from a common batch of base fuel RF06, and containing 1 ppm zinc (as zinc neodecanoate).
    [00176] Table 2 below shows the specification for the RF06 base fuel.
    [00177] The diesel fuel compositions were prepared comprising the additive components listed in table 1:

    Example 6
    [00178] Fuel compositions 1 to 3 listed in table 1 were tested according to method CECF-98-08 DW 10.
    [00179] The injector fouling test engine is the PSA DW10BTED4. In summary, the characteristics of the engine are: Design: valve control on the cylinder head with four cylinders in line, turbocharged with EGR Capacity: 1998 cm3 Combustion chamber: direct injection guided by the wall with four valves, piston cavity Force: 100 kW a 4000 rpm Torque: 320 Nm at 2000 rpm Injection system: common rail with 6 piezoelectronically controlled injectors. Maximum pressure: 1600 bar (1.6 x 108Pa). Proprietary design by SIEMENS VDO Emission control: According to Euro IV limit values when combined with the exhaust gas after-treatment system (DPF)
    [00180] This engine was chosen as a representative design of the modern European high speed direct injection diesel engine capable of meeting current and future European emissions requirements. The common rail injection system uses a highly efficient nozzle design with rounded inlet edges and tapered spray holes for optimal hydraulic flow. This type of nozzle, when combined with high fuel pressure, has advances to be achieved in combustion efficiency, reduced noise and reduced fuel consumption, but is sensitive to influences that can impair the flow of fuel, such as the formation of the deposit in spray holes. The presence of these deposits causes a significant loss of engine power and increased gross emissions.
    [00181] The test is carried out with a future injector project representative of the anticipated Euro V injector technology.
    [00182] It is considered necessary to establish a reliable baseline of the injector condition before starting the fouling tests, so a sixteen hour operating program for the test injectors is specified, using the non-fouling reference fuel.
    [00183] Full details of the CEC F-98-08 test method can be obtained from CEC. The coking cycle is summarized below. 1. A heating cycle (12 minutes) according to the following regime:
    2. 8 Hours of engine operation consisting of 8 repetitions of the following cycle:
    * for the expected range see method CEC CEC-F-98-08 3. Cool to inactivate in 60 seconds and inactivate for 10 seconds; 4. Soak period of 4 hours.
    [00184] The CEC standard test method F-98-08 consists of 32-hour engine operation corresponding to 4 repetitions of steps 1-3 above, and 3 repetitions of step 4, that is, the total test time of 56 hours excluding heating and cooling.
    [00185] In each case, a first cycle of 32 hours was carried out using new injectors and the base fuel RF-06 having added to it 1ppm of Zn (as neodecanoate). This resulted in a level of loss of strength due to the incrustation of the injectors.
    [00186] A second 32-hour cycle was then performed as a 'clean up' phase. The dirty injectors from the first phase were kept in the engine and the fuel changed to the base fuel RF-06, adding to it 1ppm of Zn (as neodecanoate) and the test additives specified in compositions 1 to 3 of table 1.
    [00187] The results of these tests are shown in figures 1 and 2. As can be seen in figure 1, the use of a combination of the quaternary ammonium salt additive B and Mannich C additive provides superior clean-up performance in a total treatment cup less than the use of the Mannich additive above.
    [00188] Figure 2 shows excellent clean-up performance using the combination of Mannich D additive and quaternary ammonium salt additive B. Example 7
    [00189] Additive E, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00190] 45.68g (0.0375 mol) of Additive A were mixed with 15g (0.127 mol) of dimethyl oxalate and 0.95g of octanoic acid. The mixture was heated to 120 ° C for 4 hours. The excess dimethyl oxalate was removed in vacuo. 35.10g of the product were diluted with 23.51g of Caromax 20. Example 8
    [00191] Additive F, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00192] 315.9g (0.247 mol) of a polyisobutyl-substituted succinic anhydride having a GDP molecular weight of 1000 were mixed with 66.45g (0.499 mol) of 2- (2-dimethylaminoethoxy) ethanol and 104.38g of Caromax 20. The mixture was heated to 200 ° C with removal of water. The solvent was removed in vacuo. 288.27g (0.191 mol) of this product was reacted with 58.03g (0.381 mol) of methyl salicylate at 150 ° C overnight and then 230.9g of Caromax 20 was added. Example 9
    [00193] The additive efficiency detailed in table 3 below in older engine types was assessed using a standard industrial test - test method CEC No. CEC F-23-A-01.
    [00194] This test measures the injector nozzle coking using a Peugeot XUD9 A / L engine and provides a means of discriminating between fuels of different propensity for the injector nozzle coking. The nozzle coking is the result of the formation of cabono deposits between the injector needle and the needle seat. The deposition of the carbon deposit is due to the exposure of the needle and injector seat to the flue gases, which potentially cause undesirable variations in engine performance.
    [00195] The Peugeot XUD9 A / L engine is a direct-injection 4-cylinder diesel engine with a displacement volume of 1.9 liters, obtained from Peugeot Citroen Motors specifically for the CEC PF023 method.
    [00196] The test engine is adjusted with clean injectors using needles from the non-flat injector. Air flow at various needle lifting positions was measured on a flow platform prior to testing. The engine is operated for a period of 10 hours under cyclical conditions.


    [00197] The propensity of the fuel to promote the formation of the deposit on the fuel injectors is determined by measuring the air flow from the injector nozzle again at the end of the test, and comparing these values to those before the test. The results are expressed in terms of the percentage of airflow reduction at various needle lifting positions for all nozzles. The average value of reduction of the air flow in needle lifting to 0.1mm from all four nozzles is considered the injector coking level for a given fuel.
    [00198] The results of this test using the specified additive combinations of the invention are shown in table 3. In each case, the specified amount of active additive has been added to an RF06 base fuel meeting the specification given in table 2 (example 5) above .

    [00199] These results show that the quaternary ammonium salt additives of the present invention used alone or in combination with the Mannich additives described here, achieve an excellent reduction in the occurrence of deposits in traditional diesel engines. Example 10
    [00200] Additive G, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00201] 33.9 kg (27.3 moles) of a polyisobutyl-substituted succinic anhydride having a GDP molecular weight of 1000 were heated to 90 ° C. 2.79 kg (27.3 moles) of dimethylaminopropylamine were added and the mixture stirred at 90 to 100 ° C for 1 hour. The temperature was increased to 140 ° C for 3 hours with concurrent removal of water. 25 kg of 2-ethyl hexanol were added, followed by 4.15 kg of methyl salicylate (27.3 moles) and the mixture maintained at 140 ° C for 9.5 hours.
    [00202] The following compositions were prepared by adding the additive G to a base fuel RF06, satisfying the specification given in table 2 (example 5) above, together with 1ppm of zinc as zinc neodecanoate.

    [00203] Composition 9 was tested according to the modified method CECF-98-08 DW 10 described in example 6. The results of this test are shown in figure 4. As this graph illustrates, excellent clean-up performance was achieved using this composition.
    [00204] Composition 10 was tested using test method CECF-98-08 DW 10 without the modification described in example 6, to measure the “keep clean” performance. This test did not include the initial 32-hour cycle using the base fuel. Instead, the fuel composition of the invention (composition 10) was added directly and measured over a 32 hour cycle. As can be seen from the results shown in figure 3, this composition performed a “keep clean” function with little change in strength observed during the test period. Example 11
    [00205] Additive H, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00206] A polyisobutyl-substituted succinic anhydride having a molecular weight of GDP of 260 was reacted with dimethylaminopropylamine using a method analogous to that described in example 10. 213.33g (0.525 mol) of this material was added to 79.82 (0.525 moles) of methyl salicylate and the mixture heated to 140 ° C for 24 hours before adding 177g of 2-ethylhexanol.
    [00207] Composition 11 was prepared by adding 86.4ppm of active additive H to a base fuel RF06 satisfying a specification given in table 2 (example 5) above, along with 1ppm of zinc as zinc neodecanoate.
    [00208] The “keep clean” performance of this composition was evaluated in a modern diesel engine using the procedure described in example 10. The results are shown in figure 5. Example 12
    [00209] Additive I, a Mannich additive was prepared as follows:
    [00210] A reactor was charged with dodecylphenol (170.6g, 0.65 mol), ethylenediamine (30.1g, 0.5 mol) and Caromax 20 (123.9g). The mixture was heated to 95 ° C and a formaldehyde solution, 37% by weight (73.8g, 0.9 mol), charged for 1 hour. The temperature was raised to 125 ° C for 3 hours and the water removed. In this example, the molar ratio of aldehyde (a): amine (b): phenol (c) was approximately 1.8: 1: 1.3. Example 13
    [00211] The raw material obtained in example 12 (additive I) and the raw material obtained in example 2 (additive B) were added to a base fuel RF06 meeting the specification given in table 2 (example 5) above, along with 1ppm of zinc as zinc neodecanoate.
    [00212] The total amount of material added to the fuel in each case was 70ppm; and the crude additives were dosed for the following reasons:

    [00213] The "keep clean" performance of compositions 12 and 13 in a modern diesel engine was evaluated using the procedure described in example 10. The results are shown in figure 6. Example 14
    [00214] The raw material obtained in example 12 (additive I) and the raw material obtained in example 2 (additive B) were added to a base fuel RF06 meeting the specification given in table 2 (example 5) above, together with 1ppm of zinc as zinc neodecanoate. The total amount of material added to the fuel in each case was 145 ppm; and the crude additives were dosed for the following reasons:

    [00215] The "keep clean" performance of compositions 14 to 17 in a modern diesel engine was evaluated using the procedure described in example 10. The results are shown in figure 7. Example 15
    [00216] The raw material obtained in example 12 (additive I) and the raw material obtained in example 10 (additive G) were added to a base fuel RF06 meeting the specification given in table 2 (example 5) above together with 1ppm of zinc like zinc neodecanoate. The total amount of material added to the fuel in each case was 215 ppm; and the crude additives were dosed for the following reasons:


    [00217] The "clean up" performance of compositions 18 and 19 in a modern diesel engine was evaluated using the procedure described in example 6. The results are shown in figure 8. Example 16
    [00218] Additive J, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00219] A reactor was charged with 201.13g (0.169 mol) of additive A, 69.73g (0.59 mol) of dimethyl oxalate and 4.0g of 2-ethyl hexanoic acid. The mixture was heated to 120 ° C for 4 hours. Excess dimethyl oxalate was removed in vacuo and 136.4g of Caromax 20 was added.
    [00220] Composition 20 was prepared by adding 102ppm of active additive J to a base fuel RF06, satisfying the specification given in table 2 (example 5) above, together with 1ppm of zinc as zinc neodecanoate.
    [00221] The “keep clean” performance of this composition was evaluated in a modern diesel engine using the procedure described in example 10. The results are shown in figure 9. Example 17
    [00222] Additive K, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00223] 251.48g (0.192 mol) of a polyisobutyl-substituted succinic anhydride having a molecular weight of 1000 and 151.96g of toluene were heated to 80 ° C. 35.22g (0.393 mol) of N, N-dimethyl-2-ethanolamine was added and the mixture heated to 140 ° C. 4g of Amberlist catalyst was added and the mixture reacted overnight before filtration and removal of the solvent. 230.07g (0.159 mol) of this material was reacted with 47.89g (0.317 mol) of methyl salicylate at 142 ° C overnight before the addition of 186.02 g of Caromax 20.
    [00224] Composition 21 was prepared by adding 93ppm of active additive K to a base fuel RF06 meeting the specification given in table 2 (example 5) above, together with 1ppm of zinc as zinc neodecanoate.
    [00225] The “keep clean” performance of this composition was evaluated on a modern diesel engine using the procedure described in example 10. The results are shown in figure 10. Unfortunately, the test failed to complete and thus the results during only 16 hours are shown. Example 18
    [00226] Additive L, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00227] A polyisobutyl-substituted succinic anhydride having a GDP molecular weight of 1300 was reacted with dimethylaminopropylamine using a method analogous to that described in example 10. 20.88g (0.0142 mol) of this material was mixed with 2.2g (0.0144 mol) of methyl salicylate and 15.4 g of 2-ethylhexanol. The mixture was heated to 140 ° C for 24 hours. Example 19
    [00228] Additive M, a quaternary ammonium salt additive of the present invention was prepared as follows:
    [00229] A polyisobutyl-substituted succinic anhydride having a GDP molecular weight of 2300 was reacted with dimethylaminopropylamine using a method analogous to that described in example 10. 23.27g (0.0094 mol) of this material was mixed with 1.43g (0.0094 mol) of methyl salicylate and 16.5 g of 2-ethylhexanol. The mixture was heated to 140 ° C for 24 hours. Example 20
    [00230] A polyisobutyl-substituted succinic anhydride having a GDP molecular weight of 750 was reacted with dimethylaminopropylamine using a method analogous to that described in example 10. 31.1g (0.034 mol) of this material was mixed with 5.2g (0.034 mol) of methyl salicylate and 24.2 g of 2-ethylhexanol. The mixture was heated to 140 ° C for 24 hours. Example 21
    [00231] 61.71g (0.0484 mol) of a polyisobutyl-substituted succinic anhydride having a GDP molecular weight of 1000 were heated to 74 ° C. 9.032g (0.0485 mol) of dibutylaminopropylamine was added and the mixture heated to 135 ° C for 3 hours with water removal. 7.24g (0.0476 mol) of methyl salicylate was added and the mixture reacted overnight before adding 51.33g of Caromax 20. Example 22
    [00232] 157.0 g (0.122 mol) of a polyisobutyl-substituted succinic anhydride having a GDP molecular weight of 1000 and 2-ethylhexanol (123.3 g) were heated to 140 ° C. Benzyl salicylate (28.0 g, 0.123 mol) is added and the mixture stirred at 140 ° C for 24 hours. Example 23
    [00233] 18.0 g (0.0138 mol) of additive A and 2-ethylhexanol (12.0 g) were heated to 140 ° C. Methyl 2-nitrobenzoate (2.51 g, 0.0139 mol) was added and the mixture stirred at 140 ° C for 12 hours. Example 24
    [00234] Other fuel compositions as detailed in table 4 were prepared by dosing the quaternary ammonium salt additives of the present invention in an RF06 based fuel meeting the specification given in table 2 (example 5) above. The effectiveness of these compositions on older engine types was assessed using the CEC No. CEC F-23-A-01 test method, as described in example 9.

    权利要求:
    Claims (16)
    [0001]
    1. Composition of diesel fuel characterized by the fact that it comprises as an additive, a quaternary ammonium salt formed by the reaction of a compound of formula (A):
    [0002]
    2. Diesel fuel composition according to claim 1, characterized in that the compound of formula (A) is an ester of a carboxylic acid having a pKa of 3.5 or less.
    [0003]
    3. Diesel fuel composition according to claim 1, characterized in that the compound of formula (A) is an ester of a substituted aromatic carboxylic acid.
    [0004]
    4. Diesel fuel composition according to claim 3, characterized by the fact that R is a substituted aryl group having 6 to 10 carbon atoms substituted with one or more groups selected from carboalkoxy, nitro, cyano, SR5 or NR5R6 hydroxy, in that R5 and R6 are each independently hydrogen or an optionally substituted C1 to C22 alkyl group.
    [0005]
    5. Diesel fuel composition according to claim 4, characterized by the fact that R is 2-hydroxyphenyl or 2-aminophenyl and R1 is methyl.
    [0006]
    6. Diesel fuel composition, according to claim 1, characterized by the fact that the compound of formula (A) is an ester of an α-hydroxycarboxylic acid.
    [0007]
    7. Diesel fuel composition according to claim 1, characterized in that the compound of formula (A) is an ester of a polycarboxylic acid.
    [0008]
    8. Diesel fuel composition according to claim 1, characterized in that R2 and R3 are each independently C1 to C8 alkyl and X is an alkylene group having 2 to 5 carbon atoms.
    [0009]
    9. Diesel fuel composition, according to claim 1, characterized by the fact that it comprises an additional additive, this additional additive being the product of a Mannich reaction between: (a) an aldehyde; (b) a polyamine; and (c) an optionally substituted phenol.
    [0010]
    10. Diesel fuel composition according to claim 9, characterized in that the component (a) comprises formaldehyde, the component (b) comprises a polyethylene polyamine and the component (c) comprises a parasubstituted monoalkyl phenol.
    [0011]
    11. Additive package, characterized by the fact that, upon addition to a diesel fuel, it provides a composition as defined in claim 1.
    [0012]
    12. Composition of diesel fuel according to claim 1, characterized by the fact that it additionally comprises a fuel based catalyst containing metals.
    [0013]
    13. Diesel fuel composition according to claim 12, characterized in that the catalyst is based on metals selected from the group consisting of iron, cerium, group I metals, group II metals, and mixtures thereof.
    [0014]
    14. Diesel fuel composition according to claim 13, characterized in that the group of metals I or group of metals II is selected from the group consisting of calcium and strontium.
    [0015]
    15. Diesel fuel composition, according to claim 12, characterized by the fact that the catalyst is selected from the group consisting of platinum and manganese.
    [0016]
    16. Use of a diesel fuel composition as defined in any one of claims 1 to 15, characterized by the fact that it is to improve the performance of a modern diesel engine having a high pressure fuel system and a traditional diesel engine
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    同族专利:
    公开号 | 公开日
    WO2011095819A1|2011-08-11|
    CA2788997A1|2011-08-11|
    GB201001920D0|2010-03-24|
    ES2655886T3|2018-02-22|
    SG182424A1|2012-08-30|
    JP2013518962A|2013-05-23|
    RU2562249C2|2015-09-10|
    CA2788997C|2018-04-24|
    EP2531580B1|2017-11-15|
    AU2011212261B2|2013-08-15|
    BR112012018408A2|2019-12-10|
    MX2012009076A|2012-08-23|
    NO2531580T3|2018-04-14|
    AU2011212261A1|2012-08-09|
    US9062265B2|2015-06-23|
    CN102844415B|2015-10-21|
    KR101818271B1|2018-01-12|
    EP2531580A1|2012-12-12|
    CN102844415A|2012-12-26|
    RU2012137255A|2014-03-10|
    AR080136A1|2012-03-14|
    US20130031827A1|2013-02-07|
    KR20120129900A|2012-11-28|
    EP3269792A1|2018-01-17|
    MY156962A|2016-04-15|
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    法律状态:
    2019-12-24| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-07-21| B09A| Decision: intention to grant|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/02/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    GB1001920.6|2010-02-05|
    GBGB1001920.6A|GB201001920D0|2010-02-05|2010-02-05|Fuel compostions|
    PCT/GB2011/050196|WO2011095819A1|2010-02-05|2011-02-04|Fuel compositions|
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