MXPA97008205A - Best combustion - Google Patents

Abstract

A process for improving the oxidation of carbonaceous products of fuel combustion and / or the improvement of fuel combustion is described. The process comprises adding to the fuel, before combustion thereof, a composition comprising at least one organometallic complex of a metal of group I or at least one organometallic complex of a metal of group II, or a mixture thereof , characterized in that the metal concentration of the organometallic complex of group I or group II in the fuel before combustion is 30 ppm or less. The organometallic complex induces an acceptable spontaneous trap regeneration according to the test protocol presented in the examples

Description

IMPROVED COMBUSTION DESCRIPTION OF THE INVENTION The present invention relates to a process for improving the oxidation of carbonaceous products derived from combustion or fuel pyrolysis (such as with the use of a particulate trap for use with diesel engines) and / or to improve fuel combustion. The combustion products of diesel fuel pyrolysis include carbon monoxide, nitrous oxides (N0X), unburned and particulate hydrocarbons. The particulates are increasingly considered as serious pollutants, to the extent that there is an increasing recognition of the health risks associated with particulate emissions. These particulates include not only those which are visible as smoke emission, but also unburned and partially oxidized hydrocarbons from the fuel and lubricants used in diesel engines. Diesel engines are susceptible to emission of high concentrations of particulate material when the engine is overloaded, worn or not properly maintained. Particulate matter is also emitted from diesel engine emissions when REF: 25995 the engines are operated at partial load although these emissions are normally invisible to the naked eye. Unburned or partially oxidized hydrocarbons that are also emitted into the atmosphere are irritating astringent materials. In addition to a problem recently brought to light for diesel fuel, particulate matter emissions of less than 10 micrometers of main dimension ("PM10 matter") are claimed to cause 10,000 deaths in England and Wales, and 60,000 deaths in the United States. annually, as published in New Scientist, March 1994, page 12. It is suspected that these smaller particles penetrate deeply into the lung and lodge there. As indicated, the emission of particulates by diesel engines is a major source of harmful air pollution, and subsequently an effective method to control particulate emissions of diesel engines has been sought. Currently there are legislations in many countries in the world designed to control the pollution of diesel engines. Stricter legislation is planned. The previous activity in the area of particle level reduction can be considered to use one of two strategies: engine design and maintenance solutions or oxidation trap solutions.

Engines that have been developed to provide low concentrations of emissions are well known to those familiar with the art and examples of such designs are provided in S.A.E. International Congress (February 1995), S.A.E. Special Publication SP - 1092. The disadvantages of the different engine maintenance solutions include cost, complexity and low retrofit capacity. Traps adapted for diesel engines have been proposed as the solution, but these normally require some input of external energy for regeneration. Such devices are well known to those familiar with the technique and some examples are discussed in "advanced techniques for regeneration in thermal trap and particulate catalytic diesel" ("Advanced techniques for thermal and catalytic diesel particulate trap regeneration", SAE International Congress (February of 1985), SAE Special Publication -42 343-59 (1992) and SAE International Congress (February 1995) and SAE Special Publication SP-1073 (1995) In addition to the need to supply an external heat source, the solutions of Oxidation in trap have similar problems, they are also susceptible to blockage of the trap and / or "chimney fires" that result from a sudden and intense combustion of soot from highly loaded traps.

Catalytic devices can help control diesel engine emissions but require a low sulfur fuel (<; 500 ppm) to allow the benefits of an exhaust gas emission to be achieved. Adhesives can be used to contribute to both strategies. In the motor maintenance viewpoints, there is a well-known balance between NOx and particulate emissions. Diesel engine emissions tests now include specified concentrations for all pollutants. An additive which achieves a certain useful concentration of particulate suppression to a certain extent uncouples this equilibrium, thereby giving the engineer more freedom to obtain a performance or power of energy or a fuel economy with a given emission standard. The use of metal-based additives within diesel fuels for these purposes is well known. However, the known additives can have numerous disadvantages. For example, some previous solutions have not considered the consequence of the potential for emissions of metals from the engine or the trap. Even the best traps can not be 100% efficient as particles to trap and therefore part of metals will be emitted. As a consequence, when toxic metals are used, always it must be doubtful whether an overall emissions benefit will be obtained. In addition, previous attempts have used relatively high dosing rates of metals, typically in the order of 50-100 ppm or greater. This has several drawbacks insofar as a larger mass of solids is finally emitted by the motor and therefore will result in a faster blockage of the trap. Unwanted deposits are also formed inside the motor, which ultimately damages the operation. In addition, previous attempts have used metals which provide products of combustion or pyrolysis, or produce species within the trap that are not volatile or that are of little or very low water solubility. As a consequence the blockage of the exit system, or more likely the oxidation trap, leads to the need for disposal or costly recycling of the trap. In addition, previous attempts have used metal additives which results in antagonistic products to the trap or to the exhaust gas system components. O-A-94/11467 for Platinium Plus describes the use of platinum compounds together with a trap to decrease the concentration of unburned hydrocarbons and carbon monoxide in the diesel exhaust gases. Lithium and sodium compounds have also been claimed as useful for lowering the regeneration temperature of the trap. There is no engine data supplied to support this claim. The teaching of this patent is that the organic salts of bit and sodium are available and are suitable for use insofar as they are soluble in the fuel and are stable in solution. There is no suggestion that any salt of a given metal works better than another salt of that metal. WO-A-92/20762 for Lubrizol discloses an arrangement of chelating functionalities with an extensive range of metals as fuel additives capable of lowering the ignition temperature of entrapped particulates within a trap. Engine data is not provided to support this claim. The complexes in the example are provided only for copper. The application describes the use of an antioxidant additive together with the metal complex as essential. No evidence is provided that the complexes are effective in the absence of this additive, that the alkaline or alkaline earth metals are all effective, or that no complex or stable soluble fuel salt can function unlike any other. DE-A-40 41 127 for Daimler-Benz discloses the use of various stable, fuel-soluble lithium and sodium salts to reduce the ignition temperature of the material retained within a diesel particulate filter. Frequent partial unlocking of the filter is observed at sodium concentrations of approximately 32 ppm / m, 28 ppm m / m with lithium. There is no suggestion that any stable salt, soluble in fuel, works better than any other; in fact, the examples given highlight the similarity of results obtained between one additive and another. O-A-95/04119 for Asociated Octel describes the use of alkali metal and alkaline earth metal salts coordinated with a Lewis base to reduce the exhaust emissions of a diesel engine. Salt complexes have the advantage of being soluble in fuel and stable. The application contains certain stipulation that such additives can be effective to catalyze the oxidation of entrapped particulates. However, no evidence is presented to support this, and furthermore, it is not described that any other additive could be more effective than any other. DE-A-20 29 804 for Lubrizol describes the use of oil-soluble carboxylic dispersants to reduce the formation of deposits in the inlet valves. There is no suggestion that the additives can remove previously formed deposits. The teaching is that there is a benefit of any emission solely from maintenance and cleaning and, as a result, the engine's designed function.

EP-A-207560 for Shell is related to the use of succinic acid derivatives and their alkali metal or alkaline earth metal salts (especially potassium) as additives to increase the flame velocity within the spark ignition internal combustion engines. . However, there is no teaching regarding the use of such additives in ignition and compression engines. EP-A-555 006 of Slovnaft AS describes the use of alkali metal or alkaline earth salts of derivatized alkenyl succinates as additives to reduce the intention of recession of valve seats in gasoline engines designed for leaded fuel, but used unleaded. GB-A-2 248 068 for Exxon describes the use of additives that contain an alkali metal, an alkaline earth metal and a transition metal to reduce smoke and particulate emissions during the combustion of diesel fuel. In accordance with the teachings of this document, the presence of a transition metal is essential. There is no teaching regarding the effectiveness of trap regeneration, or any other salt of a given metal that works better than any other. EP-A-0 476 196 for Ethyl Petroleum Additives describes the use of a three-part composition that includes a soluble and stable manganese salt, a metal alkaline or alkaline earth, soluble and stable in fuel and a neutral or basic detergent salt to reduce the concentrations of soot, particulates and the acidity of carbonaceous combustion products. There is no suggestion that an alkaline or alkaline earth metal additive, soluble in fuel, particular, works better than another. EP-A-0 423 744 describes the use of a hydrocarbon-soluble alkaline or alkaline earth metal containing the composition in the recession of the prevention valve seat in gasoline engines designed to run on leaded fuel but that bring unleaded fuel . There is no teaching in this document relevant to diesel combustion. The present invention seeks to improve the combustion of a diesel fuel in an engine combustion chamber but mainly to provide an additive which catalyzes the oxidation of soot within the trap thereby reducing what is called "ignition temperature". In particular, the present invention seeks to solve one or more of the problems associated with known fuel additives. According to a first aspect of the present invention, there is provided a process for improving the oxidation of carbonaceous or carbonaceous products derived from fuel combustion or pyrolysis (such as the use of a particulate trap for use with diesel engines), the process comprises adding to the fuel before combustion thereof, a composition comprising at least one organometallic complex of a metal of group I or at least one organometallic complex of a metal of group II, or a mixture thereof, characterized in that the concentration of the metal of the organometallic complex of group I and / or group II in the fuel, before combustion, is 100 ppm or less, preferably 30 ppm or less; and wherein the organometallic complex induces an acceptable spontaneous regeneration of the trap, according to the test protocol presented in the examples. Additionally, the process improves fuel combustion. According to a second aspect of the present invention, there is provided the use of an organometallic complex as defined in the first aspect of the present invention for improving fuel combustion and / or improving the oxidation of carbonaceous products derived from combustion or pyrolysis of the fuel (such as with the use of a particulate trap for use with diesel engines), in which the complex is added to the fuel before combustion thereof, and in which the metal concentration of the organometallic complex of group I and / or group II in the fuel, before the combustion, is 100 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less, and even more preferably 5 ppm or less. Many types of particulate traps are known to those skilled in the art and include as non-limiting examples the types of "fractured wall" and "deep bed" ceramics and types of sintered metal. The invention is suitable for use with all particulate traps; The preferred concentration of metal in the fuel is a function of the design of the trap, probably the ratio of surface area to volume. For a "deep bed" filter trap such as that built from 3M Nextel fiber, the concentration of metal in the group I and / or group II metal complex in the fuel is preferably 30 ppm or less For a filter trap of the "fractured wall" type, such as Corning EXdO ", the concentration of metal in the metal complex of group I and / or group II in the fuel is, more preferably , of 30 ppm or less. The key advantages of the present invention are that the composition can achieve improved regeneration of the traps (such as particulate traps for diesel engine) and / or improved combustion in the engines (for example in diesel engines) at low dosages in the fuel.

Additional advantages are that the additive is readily soluble in fuel and can be provided at high concentrations in a solvent miscible with the fuel. An additional advantage is that the additives are particularly stable with respect to water and therefore resistant to leaching with water. Therefore, the invention provides a composition that is very compatible with the handling, storage and supply of fuel. In particular, diesel often encounters water, especially during supply at the point of sale, and thus leach-resistant or stable compositions are beneficial. The aspect of the low dosage is particularly advantageous insofar as the present invention uses metals of known low toxicity, and preferably those which are essential for life and widely prevail in the environment. A particular advantage of the composition for use in the present invention is that it provides an additive which catalyzes the oxidation of soot within the trap thereby reducing what is called "ignition temperature" and / or improving fuel combustion. diesel. Therefore, the important advantages of the present invention include a cost efficient preparation of a diesel fuel additive that has high solubility and stability in fuel, which, when burned with fuel: reduces the ignition temperature and / or improves the oxidation of the resulting particulate material trapped inside a trap, which can revert the particulate material remaining in the gas The most collectible outlet in a trap, and / or reduce the emission of soot, unburnt hydrocarbons and partially oxidized hydrocarbons - when compared to that of a fuel burned without the preparation of additive. In this context, "regeneration" is defined as the process to reduce the pressure drop through the filter trap by oxidizing the trapped material. This usually requires some external energy input. Such filter trap devices and their regeneration means are well known to those familiar with the technique and some examples are discussed in "advanced techniques for regeneration of catalytic thermal diesel particulate traps" ("Advanced techniques for thermal and catalytic diesel particulate trap regeneration" "), SAE International Congress (February 1985) SAE Special Publication -42 343-59 (1992). However, the use of the composition according to the present invention reduces or eliminates the need for an external energy input. Another important advantage of the present invention is that under many engine operating conditions such as a result of the addition of the complex to the fuel, there is less particulate material and less remaining particulate material. Therefore, the trap can no longer be filled with particulate material. Therefore, the frequency at which the trap must be regenerated is reduced. In addition, the need for energy can be reduced or eliminated from an external source to aid regeneration. Therefore, the important advantages of the present invention include providing a fuel additive which, when burned with fuel: reduces the emission of soot, unburnt hydrocarbons and partially oxidized hydrocarbons; returns to the particulate material remaining in the most collectible exit gas in a trap; reduces the ignition temperature of the trapped material; it improves the oxidation of trapped particulate materials - when compared to the fuel burned without the preparation of additive. Burning the soot and other hydrocarbons from the surface of a post combustion or fuel pyrolysis trap comprising the composition of the present invention, therefore, provides a way to regenerate the filter and thus prevent unacceptable plugging. of particulate traps for diesel. In addition, the fuel additive of the present invention leads to reduced combustion concentrations or pyrolysis ash. Therefore, the plugging of the trap from one residue per additive is kept to a minimum. Preferably for a "deep bed" filter trap such as that built from a Nextel fiber of 3M, the concentration of the metal in the metal complex of group I and / or group II in the fuel is 30 ppm Preferably, for a "fractured wall" type filter trap such as Corning EXßO * ®, the concentration of metal in the metal complex of group I and / or group II in the fuel is 30 ppm or, preferably, the organometallic complex is stable to hydrolysis Preferably, the organometallic complex comprises a Lewis base.Preferably, the organometallic complex comprises a Lewis base and the organometallic complex is a metal complex of any of the following organic compounds: a) an aliphatic alcohol of the general formula CH 3 -X-OH, wherein X means a C 1-8 alkyl group, or a compound of such alcohol; b) an aromatic alcohol of the general formula Ph-X-OH, wherein Ph means a phenyl ring, X means an alkyl group of c) a phenol with unique substitution in the ortho, meta or para position, in which the substituted group is an alkyl group of C1-a; d) an aliphatic carboxylic acid of the general formula CH3-X-COOH, wherein X means an alkyl group of C3.16, or an isomeric compound of such a carboxylic acid; or e) a 1-naphthoic acid, a 2-naphthoic acid, a phenylacetic acid or a cinnamic acid. In an alternative embodiment, preferably the organometallic complex is a metal complex of any of the following organic compounds: a substituted aliphatic alcohol, a substituted or unsubstituted aliphatic higher alcohol (for example a diol), a substituted aromatic alcohol, a phenol substituted which comprises at least two substituted groups, a substituted aliphatic carboxylic acid, a substituted or unsubstituted aliphatic carboxylic acid (e.g., a dicarboxylic acid), or a substituted or unsubstituted aromatic acid, or derivatives thereof, but it has not been 1-naphthoic, 2-naphthoic acid, phenylacetic acid or a cinnamic acid.

Preferably, the organometallic complex is a metal complex of any of the following organic compounds: a substituted aliphatic alcohol containing ether (eg -OCH2CH2-) or amino groups, a substituted or unsubstituted aliphatic higher alcohol (eg a diol) ) containing ether (for example -OCH2CH2) or amino groups, a substituted aromatic alcohol containing groups capable of acting as Lewis base ligands (for example -NR2 or -OR), and which is in a position to form donor bonds to a metal attached to an alkoxy group, a substituted phenol which it comprises at least two substituted groups, a substituted phenol containing groups acting as a Lewis base ligand (for example -NR2 or -OR) and which are in a position to form donor bonds to a metal bond to the hydroxy phenol group, an aliphatic carboxylic acid of the general formula CH3-X-COOH, wherein X means an alkyl group with 17 or more carbon atoms, or is an alkenyl group of C3.16 or isomeric compounds thereof, an aliphatic carboxylic acid RxR2R3CCOOH wherein R1, R2 and R3 are independently selected from hydrogen, alkyl or alkenyl groups containing two or more carbon atoms, but in which one of R is hydrogen and excluding aliphatic carboxylic acids of formula to CH3-X-COOH wherein X means an alkyl group of C3_16 or alkenyl, a carboxylic acid R1R2R3CCOOH wherein at least one R is aryl or substituted aryl, and the others may be H, alkyl or alkenyl groups, except when the carboxylic acid is phenylacetic acid, a substituted or unsubstituted aliphatic carboxylic acid (eg an acid) dicarboxylic) preferably a succinic acid substituted with alkyl or alkenyl, the reaction product of a metal hydroxide with a substituted or unsubstituted aliphatic or aromatic anhydride, preferably a succinic anhydride or a β-diketone, a β-diketone replaced or a ßcetoacid. Preferably, the organometallic complex is a metal complex of a highly substituted phenol (for example, di- (t-butyl) methylphenol). Preferably, the organometallic complex is soluble in fuel. Preferably, the organometallic complex is soluble in a solvent compatible with fuel so that the organometallic complex is soluble in a proportion of 10% by weight, preferably 25% by weight, and more preferably 50% by weight or more of the solvent. Preferably, part or all of the solvent can be a polybutene. Preferably, the organometallic complex is of the formula M (R) m.nL where M is a cation of a metal alkaline or an alkaline earth metal, of valence m, not all metal cations (M) in the complex necessarily are; R is the residue of an organic RH compound, wherein R is an organic group containing an active hydrogen atom H replaceable by the metal M and linked to an O, S, P, N or C atom in the R group; n is a positive integer indicating the number of donor ligand molecules that form a bond with the metal cation, but which can be zero; and L is a species capable of acting as a Lewis base. Seen from a further aspect, the invention provides a process for regenerating the use of a particulate trap to entrap particulates in an exit gas, the process comprising burning particulates trapped in, and on the particulate trap; characterized in that at least part of the particulates comprises an organometallic complex of the formula M (R) m.nL or a compound derived from the combustion or pyrolysis of such complex in the fuel, wherein M is the cation of an alkali metal, an alkaline earth metal or a rare earth metal, of valence m, not all the metal cations (M) in the complex necessarily are the same; R is the residue of an organic compound RH, wherein R is an organic group containing an active hydrogen atom H replaceable by the metal M and linked to an atom of O, S, P, N or C in the group R; in a positive number indicating the number of donor ligand molecules that form a bond with the metal cation, but which can be zero when R comprises L; and L is a species capable of acting as a Lewis base; moreover, in which the regeneration is able to occur at less drastic or more moderate conditions (for example at a lower exit gas temperature) than when the particulates do not comprise the organometallic complex or the products of combustion or pyrolysis thereof. Preferably, R and L are in the same molecule, in which case L is, conveniently, a functional group capable of acting as a Lewis base. Preferably, the composition is metered into the fuel at any stage in the fuel supply chain. Preferably, the composition is added to the fuel close to the engine or the combustion systems, within the fuel storage system for the engine or combustor, in the refinery, in the distribution terminal or at any other stage in the chain of Fuel supply. Therefore, the present invention relates to additives for liquid hydrocarbon fuels, and to fuel compositions containing them.

The term "regeneration of a particulate trap" means cleaning the particulate trap so that it contains a minimum or no amount of particulates. The usual regeneration process includes burning out the particulates trapped inside and on the particulate trap. The regeneration of the trap is accompanied by a decrease in the resistance to gas flow (outflow) through the trap; it is detected by a decrease in the pressure drop through the trap. The term "fuel" includes any hydrocarbon that can be used to generate energy or heat. The term also encompasses fuels containing other additives such as colorants, cetane improvers, rust or rust inhibitors, antistatic agents, gum inhibitors, metal deactivators, de-emulsifiers, top cylinder lubricants and antifreeze agents. Preferably, the term encompasses diesel fuel. The term "diesel fuel" means a distilled hydrocarbon fuel or for internal combustion ignition compression engines that meet the standards established by BS 2869 parts 1 and 2, as well as fuels in which the hydrocarbons constitute a major component and fuels alternatives such as rape seed oil and rapeseed oil methyl ester. Fuel combustion can occur in, for example, a motor such as a diesel engine, or any other suitable combustion system. Examples of other suitable combustion systems include recirculating motor systems, domestic burners and industrial burners. The term "species capable of acting as a Lewis base" includes any atom or molecule having one or more pairs of electrons available according to the Lewis acid-base theory. The term "induces acceptable spontaneous regeneration of the trap according to the test protocol presented in the examples" means that the composition is highly effective, when the composition is tested according to the test protocol presented in the examples (see below) ). Therefore, the present invention relates to additives for liquid hydrocarbon fuels, and to fuel compositions containing them. In particular, the invention relates to effective additives to reduce the concentrations of particulate and / or unburned hydrocarbons in the exhaust gases. More specifically, the invention relates to additives effective to reduce the particulate matter and / or unburned hydrocarbons contained in the exhaust gas emissions of diesel engines. In addition, the invention relates to fuel additive preparations that lower the ignition temperature and improve the combustion of entrapped particulate material. Especially, the invention relates to fuel additive preparations that lower the ignition temperature and improve the combustion of trapped particulate material of diesel engines. In addition, the present invention provides fuel additives that provide a total reduction in environmental damage resulting from the combustion of that fuel. In addition to the advantages indicated above, it should be noted that when using traps with the compositions of the present invention, the need for an external energy input for regeneration is greatly reduced and, in some cases, eliminated. Therefore, the fuel additive of the present invention can be effective to reduce the exhaust emissions of the engine and especially as an auxiliary in the combustion catalyst of trapped particulate oxidation. Therefore, the additive provides a simpler, safer and less expensive form of traps to allow less frequent, less intense and less energetic regeneration, either that the heat required for regeneration is provided by the exhaust gas or by an external mechanism. In a preferred embodiment, the compositions of the present invention provide water soluble products after combustion thereof. In this regard, there is an advantage because the additive metals provide end products that are readily soluble in water so that the recycling of particulate traps becomes simpler and less expensive. In a preferred embodiment, the composition of the present invention is fuel soluble or fuel miscible. In this regard, the present invention provides concentrates of the composition (additive) in a solvent completely compatible with fuel, especially with diesel fuel, so that the fuel mixture and the additive can be carried out in a simpler and easier way. This serves to reduce the complexity and costs of any dosing device on board. In a preferred embodiment, the composition (additive) of the present invention is at least resistant, and preferably, completely inert towards leaching with water. In this regard, the present invention provides a composition that is highly compatible with the handling, storage and supply of fuel. In particular, diesel fuel frequently encounters water, especially during supply at the point of sale, and thus such compositions are of enormous benefit to this type of fuel. In one aspect of the present invention, the alkali metal and alkaline earth metal complexes of the present invention have the general formula M (R) mnL wherein M is the cation of an alkali metal or of an alkaline earth metal of valence m, R is the residue of an organic compound of formula RH, where H represents an active hydrogen atom, reactive with the metal M and linked already is to a heteroatom that is selected from O, S and N in the organic group R, or a carbon atom, so that the heteroatom or carbon atom are placed in the organic R group close to a group that extracts electrons, for example, a hetero atom or a group consisting of, or containing O, S or N or an aromatic ring, for example, phenyl, n is a number indicating the number of organic electron donating molecules (Lewis bases ) that form donor bonds with the metal cation in the complex, usually the number of up to five, more usually an integer from 1 to 4, and L is one or more organic ligand electrons (Lewis base). R may comprise one or more functional groups capable of acting as an organic stripping ligand. In a more detailed aspect, the Lewis metal-organic coordination complexes used according to the present invention contain the residue of an organic RH molecule which contains an H atom of active hydrogen which is substitutable with a metal cation. In the organic compound RH, the active hydrogen atom will be attached to a heteroatom (O, S or N) or to a carbon atom close to a group that extracts electrons. The group that extracts electrons can be a heteroatom or a group consisting of, or containing 0, S or N, for example a carbonyl group (> C = 0), thione (> C = S) or imide (> C = NH) or an aromatic group, for example, phenyl, When the group that extracts electrons is a heteroatom or a group, the heteroatom or group may be suitable in an aliphatic or alicyclic group, which, when the active hydrogen group it is an NH group, may or may not, but will usually contain this group as part of a heterocyclic ring. Suitable complexes are derivatives of a β-diketone of the formula RÍÍJCH.CÍOJR2 wherein R1 or R2 is C1-C5 alkyl, or substituted alkyl, for example, halo-, amino-, alkoxy- or hydroxyalkyl-, C3-C6 cycloalkyl, benzyl, phenyl or C1-C3 alkylphenyl, for example , tolyl, xylyl, etc., and when R1 may be the same or may be different from R2. Suitable ß-diketones include: hexafluoroacetylacetone: CF3C (0) CH2C (O) CF3 (HFA); 2,2,6,6-tetramethylheptan-3, 5-dione: (CH3) 3CC (0) CH2C (0) C (CH3) 3 If the active hydrogen atom is bound to oxygen in the organic compound RH, then the Suitable compounds include C6.30 phenolic compounds, preferably substituted phenols containing 1-3 substituents which are selected from alkyl, alkylaminoalkyl and alkoxy groups of for example cresols, guiacoles, di-t-butylcresols, dimethylaminomethylenecresol. Substituted phenols are particularly preferred. Such specially substituted metal complexes are those derived from the reaction of a metal hydroxide or other source of alkali metal or alkaline earth metal with a succinic anhydride substituted with alkyl or alkenyl, or the hydrolysis product. Typically, such anhydrides are those prepared by the reaction of isobutenes oligomerized with maleic anhydride. A wide variety of such metals and a range of techniques for their preparation are known for those skilled in the art. In general, a high molecular weight poly (isobutene) substituent provides the resulting complex with good hydrocarbon solubility at the cost of the minor metal content. We have found that the anhydride substituted with alkenyl derived from the thermal reaction of BP Napvis X-10m with maleic anhydride provides a good balance between the solubility in hydrocarbons and the metallic content. It is considered that in such compounds, a carboxylic acid group is deprotonated and binds in a similar manner to a salt with the metal ion and the second carboxylic acid group is protonated and bound to a metal ion as a Lewis base. If the active hydrogen binds to a nitrogen atom in the organic compound RH, then suitable compounds are heterocyclic compounds of up to 20 carbon atoms containing a -C (Y) -NH group as part of the heterocycle, Y is 0, S or = NH. Suitable compounds are succinimide, 2-mercaptobenzoxazole, 2-mercaptopyrimidine, 2-mercaptothiazoline, 2-mercapto-benzimidazole, 2-oxobenzoxazole. In more detail, L can be any suitable organic (suitable base Lewis) molecule, hexamethylphosphoramide (HMPA), tetra-methylethylenediamine (TMEDA), pentamethyl diethylenetriamine, dimethylpropyleneurea (DMPU), dimethylimidazolidinone (DMI), dimethyl carbonate (DMC), dimethyl sulfoxide (DMSO), dimethylformamide (DMF). Other possible ligands are diethyl ether (Et20), 1,2-dimethoxyethane (monoglyme), bis (2-methoxyethyl) ether (diglyme), dioxane, tetrahydrofuran. When R comprises L, L is conveniently a functional group capable of acting as a Lewis base donor, with dimethylaminomethyl (-CH2N (CH3) 2), ethyleneoxy (-OCH2CH20), ethyleneamine (-N (R) CH2CH2N (R ) -), carboxyl (-C02H) and ester (-C02CH2-). It should be understood that these lists are by no means exhaustive and that other suitable organic donor ligands or functional groups (Lewis bases) can be used. The metal complex will usually contain 1-4 molecules of ligand to ensure solubility in oil, that is, the value of n will usually be 1, 2, 3 or 4.

When R comprises L, n can be, and often is zero. The organometallic salt complexes of base Lewis used in the invention can be obtained by reacting a metal source M, for example, an elemental metal, with an alkyl or metal hydride, or oxide or a hydroxide, with the organic compound RH in a hydrocarbon, preferably in a an aromatic hydrocarbon solvent such as toluene, which contains the ligand in a stoichiometric amount or in an excess amount.

Although any of the alkali metals (group I: atomic numbers 3, 11, 19, 37, 55) and alkaline earth (group II: atomic numbers 4, 12, 20, 38, 56) can be used as metal (or metals) M, those complexes of sodium, potassium, strontium or calcium donor ligand are preferred. The metal hydroxide will typically be the preferred source of the metal, on an economical basis. Although the organometallic compounds described can be added directly to the fuel, either external to the vehicle or using an included dosing system or on board, preferably first they will be formulated as an additive composition for fuel or a concentrate containing the substance, or either mixtures thereof possibly together with other additives, such as detergents, defoamers, colorants, cetane improvers, corrosion inhibitors, gum inhibitors, metal deactivators, de-emulsifiers, upper cylinder lubricants, antifreeze agents, etc., in a carrier organic miscible with fuel. Without wishing to be bound by any theory, it is considered that the compositions of the present invention are effective in view of their low molecular weight and / or their smaller molecular size compared to the more commonly used overbased materials which are of nature micellar In this regard, it is considered that more "molecular" species will be distributed in a more uniform way through the fuel and therefore show greater efficiency. In addition, it is considered that the mechanisms of the type of load transfer may play a role. In this regard, the metal can act as a charge transfer agent, which causes the soot particles to acquire charge. Therefore, the tendency of similar charges to repel reduces the agglomeration of soot particles. Therefore, changes in morphology will be responsible for the easy oxidation of the particle. In addition, it is considered that the generation of hydroxyl radicals also plays a role. In this regard, metals (particularly group II) can catalyze the generation of OH radicals which are known to be important in the propagation of flame in fuel-rich flames. In addition, it is believed that the formation of combustion initiators can play a role. In this regard, the metal can form a peroxide (sodium is known to do this when subjected to combustion in air) which is particularly reactive towards carbonaceous soot and thus initiates the reaction at lower temperatures.

The present invention now describe only by way of the following non-limiting examples. In the following examples, reference will be made to the test protocol which is indicated below. This test protocol provides an easy means to determine whether a fuel additive may be acceptable as a composition in accordance with the present invention. A composition is acceptable if the composition is highly effective when the composition is tested with this test protocol. It should be noted that the claims are not limited to the compositions when they are used only in this test protocol.

PROTOCOL OF PROOF The tests are carried out on a Renault truck on a static dynamometer, whose detailed specifications are provided below.

ELABORATION: Renault 50 Series S35 vehicle REGISTERED FOR THE FIRST TIME: August 14, 1990 WEIGHT FREE OF CHARGE: 2483 KG MAXIMUM WEIGHT WITH LOAD: 3500 kg ENGINE: PERKINS PHASE 90, with normal suction, 4 cylinders in line cooled with water, compression ratio 16.5: 1 ENGINE CAPACITY: 3990 cm3 NOMINAL POWER: 62 kW at 2800 rpm CALIBER: 100 mm RACE: 127 mm FUEL PUMP: Bosch type EPVE direct injection design TRANSMISSION: Drive by means of rear wheel.

The vehicle is additionally equipped with a filter or trap for exhaust gases. The filter trap comprises XW3C-053 radial flow filter cartridges (from 3M Corporation) used in parallel - as shown in Figure 1. The cartridges are placed at the corners of an equilateral triangle - as shown in Figure 1 Nextel fiber (trademark of 3M Corporation) wound spirally around a 50 x 4 cm perforated steel tube - as shown in Figure 2 and 3 - is supplied. The cartridges are used as supplied. The distance from the engine manifold to the entrance of the trap is approximately one meter. The outlet tube and the trap are fixed with insulating material. Fuel with additive is prepared by dissolving the required amounts of additive in one liter of fuel diesel base, then diluted in base fuel until the fuel finally contains 5 ppm m / m additional metal above the base or base level. The base fuel used is BPD26, as specified below.

DIESEL ANALYSIS DESCRIPTION OF THE SAMPLE BPD26 SAMPLE NO. 944929 DENSITY @ 15 ° C 0.8415 VISCOSITY @ 20 ° C VISCOSITY @ 40 ° C 3.060 ENTURBING POINT ° C -5 CFPP ° C -14 SPILLING POINT c > C -15 IGNITION POINT ° C 70.5 SULFUR% BY WEIGHT 0.13 Initial boiling point @ ° C 185.5 VOLUME AT 5% @ c 'C 209.8 VOLUME AT 10% @ ° C 224 VOLUME AT 20% @ ° C 246.1 VOLUME AT 30 % @ ° C 260.8 VOLUME AT 40% @ ° c 271.5 VOLUME AT 50% @ ° c 280.6 VOLUME AT 65% @ ° c 294.8 VOLUME AT 70% @ ° c 299.6 VOLUME AT 85% @ ° c 319.8 VOLUME AT 90% @ ° c 330.1 VOLUME AT 95% @ ° c 347.0 FBP @ ° c 360.4% RECOVERY VOLUME 98.1% WASTE VOLUME 1.8% WASTE VOLUME 0.1 CCI (IP41) 54.5 C.C. I. (IP380) 53.2 CETANEO IMPROVEMENT-% NOTHING CETANUM NUMBER 54.2 The test is done in two parts; A phase of soot collection or trap blocking, and A stage of forced filter regeneration or burnout. The soot collection phase consists of operating the truck at a stable speed and a load carrying load at level for the unloaded vehicle so that, for a clean trap, the outlet gas temperature is approximately 195 ° C. the entrance of the trap. This handling condition is continued until the accumulation of soot causes a pressure drop through the filter that reaches a value of 200 mbar (150 mbar are used during some early runs). The regeneration stage of the forced filter includes increasing the temperature of the outlet gas until the soot collected in the trap ignites and is eliminated by burning. This occurs when the vehicle speed increases to approximately 90 km / h and the load of the dynamometer to 300 Nm at 5 Nm / minute. This is done at the end of each soot accumulation phase, that is, when the pressure drop reaches 200 mbar. Soot ignition is inferred by observing a decrease in the pressure drop across the filter. "Forced" ignition produces at exit gas temperatures of > 300 ° C. "Spontaneous" burnout or ignition is that occurring at or below approximately 200 ° C. Each run sequence using fuel with a given additive is preceded by a minimum of three trap lock sequences and removal by soot or regeneration, as described in the above. For this base, untreated fuel is used. Typically, outlet gas temperatures between 500 and 550 ° C are reached. The time to load the trap decreases with successive runs using base fuel (reference fuel data). Runs using fuel with additives are characterized by the spontaneous ignition of the soot and prolonged soot collection phases are observed to reach the "blocked" condition. The degree to which these phenomena are observed varies between one fuel with additive and another. The additives are characterized as follows. 1. An additive is considered to be "highly effective" if two or fewer soot accumulation and filter regeneration sequences are required before a period of soot collection run prolonged, that is, more than 12 hours, which is obtained without the need for forced regeneration; typically ten or more spontaneous ignitions of soot is observed 5 when this is obtained. 2. It is considered an additive that is "low effective" if the previous conditions regarding the run for prolonged soot collection and / or the number of forced regenerations required, however some spontaneous ignitions are observed. 3. An "ineffective" additive is considered if, after running five sequences of soot collection and forced burning elimination, no episodes of spontaneous ignition or ignition have been observed. extended run, that is, more than six hours.

Example 1: Preparation of the 1,3-dimethylimidazolidinana adduct of 2, 2, 6,6-tetramethylheptan-3,5-sodium dioneate: [Na (TMHD) .EMI] A round bottom flask is charged under nitrogen with sodium hydride (NaH, 4.8 g, 200 mmol), dry toluene (100 cm3) and dimethyl imidazolidinone (23.8 cm3, 22.8 g, 200 mmol). Subsequently, 2, 2, 6,6-tetramethylheptan-3,5-dione (HTMHD, 43 cm 3, 37.97 g, 206 mmol) is added dropwise to a nitrogen discharge. After the addition of some drops effervescence is observed. The solution is stirred and heagently (oil bath, 60 ° C) for one hour, before filtration. A yield higher than 90% of NaTMHD.DMI crystals grow when refrigera Melting point 70-72 ° C, C / H / N found versus (calcula% by weight, C 60.09 (60.00), H 9.14 (9.06) and N 8.67 (8.85), H NMR in C6D6 deviations relato TMS 5.873 ppm (s, H, COCHCO), 2,609 (s, 6H, NCH 3), 2,570 (s, 4H, CH 2 CH 2) and 1,396 (s, 18H, C (CH 3) 3).

Example 2: Preparation «5n« of the sodium salt of poly (isobutyl enyl) succinic acid, approximately 1000 molecular weight [NaIPIBSAOoo]] A suspension of solid sodium hydroxide powder (8.04 g, 200 mmol) in a solution of poly (isobutenyl) succinic anhydride (PIBSA, 198.8 g, 200 mmol) in dry toluene (995 cm3) is allowed to stir at room temperature. environment for several days. The solids are dissolved to provide a clear solution of poly (isobutenyl) succinic acid of molecular weight 1000, as a monosodium salt.

Example 3: Preparation of the dixethylcarbonate adduct of the sodium salt of 2,6-diter-butyl-4-methylphenol [(NaBHT) 2.3 DMC] A solution of 2,6-diter-thiaryrylbutyl-4-methylphenol (butylahydroxytoluene, BHT, 21.8 g, 100 mmol) in dry toluene (100 cm3) is added to a suspension of sodium hydride (2.4 g, 100 mmol) in dry toluene (100 cm3) and dimethyl carbonate (12.64 cm3, 13.51 g, 1.5 equivalents) under an inert atmosphere. The precipitation of the white material is accompanied by production of hydrogen gas and heat. After the addition is complete, the reaction mixture is stirred at room temperature for approximately 60 minutes. The solids are isolaby filtration and dried under vacuum.

C / H / N found versus (calcula% by weight, C 62.40 (62.07) and H 8.28 (8.49).

Example 4: Preparation of the d-uenetyl dazolidinana adduct of the strontium salt of 2,2,6,6-tetramethylheptane-3,5-dione; [Sr (TMHD) 2.3DMI] HTMHD (21 cm3, 18.54 g, 100.6 mmol) is added under an inert atmosphere to a solution of di-ethyl imidazolidinone (30 cm3, 32.32 g, 283 mmol) in dry toluene (20 cm3) containing one piece (6 g) of metal of strontium. Immediate effervescence is observed. The contents of the flasks are stirred and hea(80 ° C, oil bath) overnight, which provides a yellowish solution and some colorless solids. The solids are dissolved by the addition of additional toluene (30 cm3) and the unreacSr is removed by filtration. The cooling provides large brick-shaped crystals of [Sr (TMHD) 2.3DMI] with a yield of 90%.

EXAMPLE 5: Pr-eparation of the strontium salt of poly (isobutenyl) succinic anhydride of molecular weight 1000 [SIPPIBSAiooo],] Poly (isobutenyl) succinic anhydride of molecular weight 1000 (69.48 g, 69 mmol) is weighed into a round bottom flask. Dry toluene (347 cm3) is added. The mixture is heated and stirred to form a homogeneous solution. Then strontium hydroxide octahydrate (6.90 g, 26 mmol) is added cautiously. Some foam formation accompanies the addition. The mixture is refluxed for one hour and then left stirring overnight. Then a Dean-Stark apparatus is used to remove 3.8 cm3 of water. The resulting slightly cloudy solution is filtered, and 0.7 g of solids are recovered. A final solution concentration of 0.56% by weight of Sr as Sr (PIBSA1000) 2 is obtained.

Example 6: Preparation of the adduct of di-methyl-unidazole? -inone of calcium bis 2,2 / 6,6-tetramethylheptan-3,5-dioneate [Ca (TMHD) 2.2D I].

It allows a suspension of calcium hydride (0.42 g, 10 mmol) in toluene (30 cm3) in the presence of two equivalents of dimethylimidazolidinone (2.2 cm3, 20 mmol), react with four equivalents of 2,2,6,6-tetramethylheptan-3,5-dione (40 mmol, 8.4 cm 3). After the initial exotherm is turned off, the mixture is stirred and heated gently to provide a clear solution. The solution is filtered, reduced in volume until crystals begin to appear, then heated to re-dissolve the crystals. The recrystallization is then found on cooling.

Ej < Example 7: Preparation of 1,3-diimethylimidazolidinone (DMI) adduct of potassium 2,2,6,6,6-tetramethyl-3,5-heptanedione: [. { K (TMHD)} 2.EMI] Potassium hydride (KH, 0.90 g, 22.5 mmol) is washed of mineral oil, dried and placed in a tube Schlenk. Then hexane is added followed by DMI (7 ml, 64. 22 mmoles). There is a certain effervescence, which implies the reaction or dissolution, and a green coloration is evident. Subsequently, TMHD (4.4 ml, 21.05 mmoles) is added slowly, as a very vigorous reaction takes place. After approximately 15 minutes the reaction subsists and an oil is sedimented from the solution. The two-phase liquid is cooled in a box with ice (at -10 ° C) and a solid crystalline mass is formed from the oily part in about half an hour.

The crystalline solids are washed with hexane, isolated and determined to be an adduct of dimethylimidizolidinone of 2, 2, 6,6-tetramethylheptan-3,5-dione potassium: [. { K (TMHD)} 2. DMI]. Yield, 1.7 g, 16% of the first batch, based on a 1: 2 ratio of 1: donor.

Formula: K [(CH3) 3C (-0) CH2C. { = 0) C (CH3) 3] .0 = CN (CH3) CH2CH2N (CH3), p.m. 450,678 p.f. 64-68 ° C Example 8: Dimethylimidazolidinana adduct of 2, 6-diter-butyl-4-methylphenol "of potassium, [K (BHT) .2EMI].

The method of Example 4 is used, with the appropriate change in the Lewis base: metal ratio. The adduct is sufficiently soluble in toluene to allow recrystallization. The microcrystals obtained have a melting point of 92-96 ° C.

Example 9: Dimethylimidazolidinone adduct of sodium 2,6-ditert-butyl-4-methylp-enol, [Na (BHT) .3EMI].

The method of Example 4 is used, with the appropriate change in the Lewis base metal ratio. The adduct it is sufficiently soluble in toluene to allow recrystallization. The obtained crystals have a melting point of 96-98 ° C.

Example 10: Dimethylimidazolidinedione adduct of sodium 2-methoxyphenol, [Na (TMP) .EMI].

The method of Example 4 is used, with the appropriate change in the Lewis base: metal ratio. The adduct is sufficiently soluble in toluene to allow recrystallization. The obtained crystals have a melting point of 87-89 ° C.

Example 11: Adduct of di-methylimidazolidone of strontium bis-2,4,6-trimethylphenol, [. { SrClMP) 2} 2.5EMI].

The method of Example 4 is used, with the appropriate change in the proportion of Lewis base and phenol: metal.

The adduct is sufficiently soluble in toluene to allow recrystallization. The crystals similar to fine needles obtained have a melting point of 244 ° C.

Ex-amp 12: Preparation of the sodium salt of poly (isobutenyl) succinic anhydride of molecular weight 420.

A thermoset reactor "Soverel" ** is charged with Hyvis BP XD-35mr poly (isobutene) (665.79 g, average number of molecular weight, 320, 2.08 moles) and maleic anhydride (411.79 g, 4.2 moles, 2.02 equivalents). The contents are heated to 200 ° C with oil flowing through a jacket through an external oil bath and stirred vigorously for 8 hours. A viscous dark brown solution is formed. The unreacted maleic anhydride is removed under vacuum, together with parts of the unreacted poly (isobutene). A material that is analyzed is recovered as 11.2% by weight of poly (isobutene). A sample of the material prepared before (535.78 g, theoretical 1.125 moles of PIBSA420) is charged in a flat-bottomed glass vessel, fitted with a turbine agitator, with a thermocouple well and loading orifice. The container is additionally charged with Solvesso 150 ™ * (502.26 g). The content is heated to 82 ° C by means of an external oil bath which is stirred until homogeneous. Subsequently, sodium hydroxide is loaded in the form of lentils (46.03 g, 1.15 mol). The resulting suspension of 1 mm white spheres in brown solution is stirred overnight at 78 ° C. A material (1066.19 g) containing 2.13% by weight of sodium is obtained as poly (isobutenyl) succinic acid with molecular weight 420.

Example 13: Pr-spacing of poly (isobutylene) -succinic anhydride of average molecular weight number 420 -PIBSA ^.

A reactor is charged with BP-Hyvis XD-35mr poly (isobutylene) (12,906 kg, 40.33 moles) and heated to 100 ° C with shaking before adding maleic anhydride (5,966 kg, 60.88 moles). The temperature of the oil bath that supplies the jacket of the reactor is set to 220 ° C, the internal temperature of the reactor reaches 185 ° C after three hours. This is considered as the beginning of the reaction time. The temperature of the oil bath is lowered to 212 ° C and the reaction mixture is stirred for about 30 hours. At the end of this period vacuum is applied and excess maleic anhydride is distilled off. After 15 hours under vacuum, the residual content of maleic anhydride is 0.0194% by weight and residual PIB of 19.9% by weight. Approximately 13,888 kg of a brown viscous material are recovered.

Example 14: Preparation of the strontium salt of PIBSA * 20 ' A reactor is charged with material prepared in example 13 (555.81 g, 445.99 g, 1.06 moles of PIBSA420, 109.82 g, 343 mmoles of PIB320) and Solvesso 150MR (346.46 g).

This mixture is stirred and heated to homogeneity. Subsequently, strontium hydroxide octahydrate (140.43 g, 0.53 mol) is added and heated at 50 ° C overnight. The water (40.62 g) is removed by heating the solution to 120 ° C. The product contains 5.36% by weight of Sr as Sr (PIBSA420) 2.

Example 15: Preparation of the potassium salt of PIB-SA ^ A reactor is charged with oil chag eta, with a material prepared in Example 13 (440.78 g, 0.85 moles of PIBSA420), and Solvesso 150"(462.53 g) .The contents are heated to 50 ° C and stirred until homogeneous. Then KOH flakes (47.88 g, 0.77 mole of 10% H20) are added with stirring, and the resulting suspension is allowed to stir overnight.The solids dissolved in FTIR analysis show an absence of absorption of 1863 cm. 1 due to PIBSA. The solution contains 3.33% by weight of K as K (PIBSA420).

Example 16: Pr-eparation "of poly (isobutylene) -succinic anhydride with average number of molecular weight of 360 (PIBSA ^ o).

A poly (isobutylene) of average molecular weight number 260 (PIB260, BP-Napvis X10MR, 586.2 g, 2.257 moles) is charged in a one liter reaction vessel, with oil jacket. The vessel is further charged with maleic anhydride (442.71 g, 4.52 moles). The mixture is heated to 200 ° C and stirred for 24 hours. At the end of this period, the maleic anhydride is removed by vacuum distillation. A dark brown viscous oil is recovered and analyzed by determining as PIBSA360 containing 8.1% m / m of PIB260.

Example 17: Preparation of the sodium salt of poly (isobutylene) succinic acid "of average molecular weight number 360 - Na (PIBSA-360) A reactor is charged with a sample of poly (isobutylene) succinic anhydride prepared as in the above (412.91 g, 392.26 g of PIBSA360, 1.096 moles, 20.65 g of GDP260). The container is additionally charged with Solvesso 150"* (526.19 g) and the liquids are heated and agitated to form a homogenous dark brown solution. Then sodium hydroxide is added as dry granules (43.84 g, 1096 moles). The resulting suspension is stirred overnight at 70 ° C. The FTIR indicates complete consumption of PIBSA and the formation of carboxylic acid and carboxylic acid salt. The solution is decanted and analyzed, determining that it contains 2.35% by weight of Na as Na (PIBSA360).

Ex «amp 18: Preparation of the strontium salt of poly (isobutylene) succinic acid with average molecular weight number 360 - Sr (PIBSA-360) 2 A jacket reactor is charged with poly (isobutylene) succinic anhydride prepared as in Example 16 (468.43 g, 451.10 g, 1.26 moles of PIBSA, 37.33 g of PIB) and Solvesso 150"* (568.90 g), both are heated at 50 ° C and stirred to provide a homogeneous solution, Sr (0H) 2.8H20 (170.79 g, 0.64 mole) is then added The resulting suspension is subsequently stirred until the solids have dissolved. Water.

Ex «Comparative breath 1: Pr-eparation of the sodium salt of ter-amyl alcohol [NaOtAm], as a 20% by weight solution in xylene Sodium stored under mineral oil is cleaned of the oxide / hydroxide outer layer and then cut into 1 cm cubes under toluene. The pieces are stirred dry in air, then charged (50.27 g) in an electrically heated, tared container equipped with nitrogen discharge and a carrot valve. The sodium is melted and then added via a valve under an inert atmosphere to a round bottom flask containing dry mixed xylenes (400 g, 465 cm 3), there are 38.45 g (1.67 moles) which have been transferred in this manner. Subsequently, additional dry mixed xylenes (175 cm3, 152 g) are added to the reaction flask. The heated container is then replaced with a reflux condenser. The reaction flask is further adjusted with a pressure equalizing dropping funnel. The flask is heated in an oil bath until the sodium melts. Rapid agitation provides a silvery suspension. The dropping funnel is charged with teramyl alcohol (182 cm3, 155 g). The alcohol is added with caution for approximately thirty minutes. A moderate production of hydrogen is observed. The reaction is heated with stirring during about 18 hours, during which time a clear and colorless solution is produced. The solution is transferred through a cannula to dry flasks which are then sealed tightly to prevent the ingress of oxygen or moisture.

Comparative Example 2: Preparation of sodium dodecylbenzene sulfonate sobr based eight times with sodium carbonate A stable dispersion is prepared in mineral oil of overbased sulphonic acid, as described in GB 1481553, except that poly (isobutenyl) succinic anhydride of average molecular weight 1000 (142 g) versus 560 (71 g) is used, Comparative Example 3: sodium t-er-butoxide in prop.an-2-ol All appliances are dried in an oven at 120 ° C and cooled under a nitrogen flow or during admission in a dry box. A round bottom flask is charged in the dry box with sodium tert-butoxide powder (20126 g, Aldrich, fresh flask). The flask is capped and removed from the dry box and fitted with nitrogen discharge, an overhead stirrer and a drip funnel. pressure equalized. The dropping funnel is then charged with anhydrous propan-2-ol (820.94 g, Aldrich) by means of a cannula from a "Sure-Seal" bottle. * The alcohol is added slowly with stirring and gentle heating to the alkoxide. produces a clear, light green solution.

R «eduction« sn the output of Emissions in the Motor The engine used for the test is a single cylinder version of a direct injection engine normally aspirated Perkins 4-236. This engine is mentioned elsewhere as a Perkins 236-S engine. The engine is arranged so that only the cylinder closest to the daisy is operational. The fuel pump is a Simms funnel unit that will be operated to supply the ignition cylinder. The fuel system is arranged in a way that allows easy fuel change without contamination of one fuel with another.

The fuel is mixed by conventional methods to contain 10 ppm m / m of additive metal. The motor is connected to a current eddy dynamometer Heenan & Froude controlled by a test bed control system. The speed of the motor and the dynamometer can be measured by magnetic pickup and an arrangement of 60 tooth wheel. A load cell is placed to indicate the torque torque adsorbed by the dynamometer. The air inlet of the engine is conditioned by a special purpose unit to humidify and ensure that the air supply is maintained at a constant temperature. The test bed is equipped with a computer-based data collection system. The smoke measurements are carried out by a Celesco Model 107 obscuration type smoke meter having a light path of 100 mm. A Bosch smoke meter is also used to extract a liter of exhaust gas through a standard filter paper. A Bosch monitoring unit is used to classify the blackening of the filter paper. Unburned hydrocarbons are determined by making a sample of the exhaust gas through a pipe heated to a flame ionization detector Beckman (FID model 402). The hydrocarbons are measured in terms of one carbon equivalent. The base fuel is BPD25 as described below.

ANALYSIS OF DIESEL DESCRIPTION OF THE SAMPLE BPD25 SAMPLE NO. 933117 DENSITY @ 15 ° C 0.8373 VISCOSITY @ 20 ° C VISCOSITY @ 40 ° C 2.988 POINT OF BURNING ° C -3 CFPP ° C -17 POINT OF SPILL ° C -21 POINT OF IGNITION ° C 67 SULFUR% IN WEIGHT 0.17 FIA : -% SATURATED VOLUME 73.2% OLYMPIC VOLUME 1.3% AROMATIC VOLUME 25.5 177.3 VOLUME AT 5% @ c • c 199.9 VOLUME AT 10% @ ° C 212.9 VOLUME AT 20% @ ° C 237.2 VOLUME AT 30% @ ° C 255.1 VOLUME AT 40% @ ° c 268.8 VOLUME AT 50% @ ° c 279.8 VOLUME AT 65% @ ° c 295 6 VOLUME AT 70% @ ° c 301 1 VOLUME AT 85% @ ° c 324 2 VOLUME AT 90 % @ ° c 334 5 VOLUME TO 95% @ ° c 350, 7 FBP @ ° c 363.9% OF VOLUME OF RECOVERY 98.6% OF VOLUME OF WASTE 1.4% OF VOLUME OF LOSS 0.0 CC I. (IP 218) C.C. I. (IP 364) 53.9 CETANE IMPROVEMENT - CETANE IMPROVING TYPE -% NOTHING NUMBER OF CETANUS 52.3 The following data was obtained at an engine speed of 1350 rpm, with a load of 55 Nm Additive Example Reduction of untreated fuel, with respect to the base (%) Smoke and hydrocarbon emissions Bosch Celesco HC NaTMHD. DMI 1 5.3 11.8 14.2 NaTMHD. DMI 1 10.2 13.7 28.6 average 7.8 12.8 21.4 Sr (TMHD) 2.3DMI 4 3.4 9.3 6.2 Sr (TMHD) 2.3DMI 4 8.6 7.1 10.1 Sr (TMHD) 2.3DMI 4 6.7 7.6 5.6 media 6.2 8.0 7.3 Ca (TMHD) 2.2DMI 6 2.0 5.3 -3.4 K (TMHD) .0.5DMI 7 2.7 17.9 25.0 K (BHT) .2DMI 8 10.4 3.7 12.2 The following data was obtained from the same system, at an engine speed of 1350 rpm, by varying the load on the dynamometer, as described in the table.

Compound / Reduction of untreated fuel with (Example) with respect to base (%) Smoke detected by Bosch 10 Nm 20 Nm 30 Nm 40 nM 50 Nm maximum torque Na (TMHD) .DMI (1) 23 33 30 37 - 1 - 13 Sr (TMHD) 2.3DMI (4) 58 0 11 35 0 1 K (TMHD) .0.5DMI (7) 48 39 31 15 8 7 K ( TMHD) .0.5DMI (7) 43 33 36 - 9 - 1 8 K (BHT) .2DMI (8) 20 29 20 2 4 6 Na (TMP) .DMI (19) 46 16 44 22 - 5 - 6 Smoke reduction tests in static motors Examples of PIBSA of metal, all prepared from PIBSA obtained as in example 13 from the maleinization of BP Hyvis XD-35"*, are added to commercial diesel fuel shaped to BS 2869 to provide metal concentrations of 10 mg / kg of fuel and tested on a single-cylinder, static, Perkins 236-S DI engine, the mixing data is as follows: Metal Prepared by Atomic Weight Compound Method Metal mg / ml of the metal method mg / kg mg / kg combustible fuel fuel Example 14 87.62 294.0 10 8.5 Na Example 12 22.99 502.5 10 8.5 K Example 13 39.10 293.0 10 8.5 The engine runs at a constant speed of 1400 rpm at a brake load of 55 Nm. The engine is run with base fuel (without additive) then it is changed to work with fuel with additive, then it is returned to work with the base fuel, then with the fuel with additive and so on during the test period. Smoke emissions are measured using an AVL 415 smoke meter. In this method, a volume of gas is drawn through a filter paper and the filter smoke number (FSN) is obtained optically as a reduced reflectance function. A large number of measurements are taken for each fuel, the FSN reduction is defined as the difference between average FSN in the fuel with additive and the average FSN in the adjacent base fuel test (as a percentage of the base fuel test FSN ). A series of such tests is carried out with each additive and the average reduction is shown in the following table; Metal Prepared by the% reduction method of FSN Sr Example 14 12.3 Na Example 12 7.1 K Example 13 10.3 The above data shows that the additives of the invention are effective as reducers for engine emissions, in a diesel engine system.

Pru «engine mounts The compounds and compositions of the examples mentioned above are tested in accordance with the test protocol mentioned above.

The compounds tested in chronological order were: [Na (PIBSA1000)] (Example 2), [Nate amylate] (Comparative Example 1), [. { Na (BHT)} 2.3DMC] (Example 3) [Sr (PIBSA1000) 2] (Example 5), [Sr (TMHD) 2.3DMI [(Example 4), [Na (TMHD) .DMI] (Example 1), Overbased sodium dodecylbenzenesulfonate (Comparative Example 2), and NaOtBu in propan-2-ol, (as described in DE-A-4041127) (Comparative Example 3).

During the trial period, the cumulative total distance exceeds 30,000 km. As the test progresses, the soot accumulation time with the base fuel increases, that is, it becomes more difficult to eliminate the memory or remnants of fuels with additive. A typical soot collection operating sequence in the base fuel is 5.14, 2.78, 2.18, 1.42 and 0.80 hours.

Results For sodium ter-amylate (Comparative Example 1) the soot collection shift times to reach 200 mBar are: 0.72, 2.10, 1.80, 9.68 and 4.52 hours. According to the protocol, the additive is considered to be of low effectiveness.

The overbased sodium dodecylbenzenesulfonate (Comparative Example 2) requires two soot accumulation and burn-off sequences, after which it can run for about 12 hours. The operation is marginal; On two occasions the outlet pressure reaches 200 mBar. The additive is of low effectiveness. For sodium butyrate in isopropanol (Example Comparative 3), the soot collection shift times to obtain 200 mBar were: 2.85, 2.61, 2.46, 6. 34, 2.53 and 2.22 hours. According to the protocol, this additive is also classified as ineffective. All the other compounds tested were highly effective in avoiding filter blockage, according to the test protocol. Here the additives are classified according to the average pressure drop through the trap. A low pressure drop reflects ability to maintain the cleanliness of the trap.

Example Order Compound Fuel Time of N No. of regenerations Medium trap Classification Bat No. operation f? s (mBar) 1 3. { Na (BHT); 3DMC 950790 18 00 1 65 2 1 NafTMHDI.DMI 951398 24.00 1 79 3 2 Na PIBSA 950705 17.75 1 80 C3 Na sulfonate 951811 12.00 104 overbased 5 44 SSrrftTTMMHHDDII ^^ DDMMII 995511332266 2200..2244 2 116 6 55 SSrrIIPPIIBBSSAA)) ,, 1122..5566 1 117 Pru «sba of Trap Regeneration Using Fractured Wall Trap A Peugeot 309 diesel engine, specified as indicated below, is operated in the manner described in the test protocol, except that no base fuel is used and the "Nextel ™" fiber trap is replaced by a "fractured wall" trap. "prepared from Corning EXdO." It is found that higher dose rates are required in order to obtain a regeneration "spontaneous" of the trap (ie, regeneration without the need to increase the speed of the motor and the load).

The sodium in the fuel is mixed as the salt prepared by the method of example 17. The results are presented in the form of peak back pressure and the corresponding outlet gas temperature at the entrance of the trap at the beginning of the spontaneous regeneration of the trap. .

Model 309D Body with 4 seats Disposition Drive with front wheel Weight Kerb kg 990 Engine type Diesel indirect injection Sweeping volume 1,905, normally aspirated Compression ratio 23.5: 1 Caliber, stroke mm 83, 88 Rotodiesel fuel pump Rotary type Transmission 5 manual speeds Test No. Concentration Temperature Back pressure, mBar of sodium ppm ° C 960663 25 < 200 < 200 960729 17 < 210 < 200 The acceptable temperature and pressure for spontaneous regeneration are within the design and operating philosophy of the trap / motor combination, in particular the fuel consumption penalty, due to the back pressure, which is considered acceptable. Other modifications will be apparent to those familiar with the art without departing from the scope of the present invention.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (41)

K2MES

1. A method for regenerating a particulate filter trap, the method is characterized in that it comprises adding to a fuel, before combustion thereof, a composition comprising an organometallic complex consisting essentially of a Group II metal, characterized in that the concentration of the metal of the organometallic complex in the fuel, before combustion, is 100 ppm or less.

2. The method according to claim 1, characterized in that the metal concentration of the organometallic complex in the fuel, before combustion, is 30 ppm or less.

3. The method according to claim 1 or claim 2, characterized in that the filter trap is a ceramic monolithic type trap and the metal concentration of the organometallic complex in the fuel, before combustion, is 30 ppm or less.

4. The method according to claim 1 or claim 2, characterized in that the filter trap is a deep-bed trap and the concentration of the organometallic complex in the fuel, before combustion, is 30 ppm or less.

5. The method according to any of the preceding claims, characterized in that the organometallic complex comprises a complex of Sr and / or Ca.

6. The method according to any of the preceding claims, characterized in that the organometallic complex is stable to hydrolysis.

7. The method according to any of the preceding claims, characterized in that the organometallic complex comprises a Lewis base.

8. The method according to any of claims 1 to 7, characterized in that the organometallic complex comprises a metal complex of any of the following organic compounds: a substituted aliphatic alcohol, an optionally substituted aliphatic higher alcohol, a substituted aromatic alcohol, a substituted phenol comprising at least two substituted groups, a substituted aliphatic carboxylic acid, an optionally substituted aliphatic higher carboxylic acid or an optionally substituted aromatic acid, or derivatives thereof, but not 1-naphthoic acid, 2-naphthoic acid, phenylacetic acid or cinnamic acid.

9. The method according to claim 8, characterized in that the organometallic complex comprises a metal complex of any of the following organic compounds: a substituted aliphatic alcohol containing ether or amino groups, an optionally substituted aliphatic higher alcohol containing ether or amino groups, a substituted aromatic alcohol containing groups capable of acting as Lewis base ligands and capable of forming donor bonds with a metal attached to the alkoxy group, a substituted phenol comprising at least two substituted groups, a substituted phenol containing groups capable of acting as Lewis base ligands and capable of forming donor bonds to a metal attached to the hydroxyphenol group, an aliphatic carboxylic acid of the general formula CH 3 -X-COOH wherein X means an alkyl group with 17 or more carbon atoms, or is an alkenyl group of C3.16 or isomeric compounds thereof, a carboxylic acid aliphatic boxyl R ^ R ^ COOH wherein R1, R2 and R3 are independently selected from hydrogen or alkyl groups containing two or more carbon atoms but in which no more than R1, R2 and R3 is hydrogen and excluding aliphatic carboxylic acids of formula CH3-X-COOH in which X means an alkyl group of C3-16, a carboxylic acid R1R2R3CCOOH in which at least one of R1, R2 and R3 is aryl or substituted aryl and the others may be H or alkyl groups, except when the carboxylic acid is phenylacetic acid, and an optionally substituted higher aliphatic carboxylic acid.

10. The method according to claim 9, characterized in that the organometallic complex comprises a metal complex of an optionally substituted aliphatic dicarboxylic acid in which both carboxyl groups are capable of interacting with the same metal ion.

11. The method according to claim 10, characterized in that both hydroxyl groups are the reaction products of a metal hydroxide with an optionally substituted aliphatic or aromatic anhydride, before or after hydrolysis.

12. The process according to claim 10, characterized in that both carboxyl groups comprise substituted succinic acids, succinic anhydrides, a β-diketone, substituted β-diketone or β-ketoacid.

13. The method according to any preceding claim, characterized in that the organometallic complex comprises an alkaline earth metal salt of a succinic acid substituted with alkyl or alkenyl.

14. The method according to claim 7, characterized in that the organometallic complex comprises a metal complex of any of the following organic compounds: a) an aliphatic alcohol of the general formula CH3-X-0H, wherein X means an alkyl group of C1-8, or a compound of such alcohol; b) an aromatic alcohol of the general formula Ph-X-OH, wherein Ph means a phenyl ring, X means an alkyl group of C ^; c) a phenol with unique substitution in the ortho, meta or para position, in which the substituted group is an alkyl group of C1.B; d) an aliphatic carboxylic acid of the general formula CH3-X-COOH, wherein X means an alkyl group of C3.16, or an isomeric compound of such a carboxylic acid; or e) a 1-naphthoic acid, a 2-naphthoic acid, a phenylacetic acid or a cinnamic acid.

15. The method according to claim 8 or claim 9, characterized in that the organometallic complex comprises a metal complex of a highly substituted phenol.

16. The method according to claim 15, characterized in that the organometallic complex is a metal complex of di- (t-butyl) ethylphenol.

17. The method according to any of the preceding claims, characterized in that the organometallic complex is soluble in fuel.

18. The method according to any of the preceding claims, characterized in that the organometallic complex is soluble in a compatible solvent in fuel in the measure of 10% by weight or greater.

19. The method according to claim 18, characterized in that the organometallic complex is soluble in the solvent in the amount of 25% by weight or greater.

20. The method according to claim 18, characterized in that the organometallic complex is soluble in the solvent to the extent of 50% by weight or greater.

21. The method according to any of the preceding claims, characterized in that the organometallic complex is of the formula M (R) m.nL in which M independently represents a cation of an alkaline earth metal, of valence m; R is the residue of an organic compound RH, wherein R is an organic group containing an active hydrogen atom H replaceable by the metal M and linked to an atom of O, S, P, N or C in the group R; n is a positive integer indicating the number of donor ligand molecules that form a bond with the metal cation, but which can be zero; and L is a series capable of acting as a Lewis base.

22. The method according to claim 21, characterized in that R and L are present in the same molecule.

23. The method according to claim 21 or claim 22, characterized in that M (R) m.nL is derived from the reaction of an anhydride alkylsuccinic or alkenylsuccinic, or of its hydrolysis product with a group II metal hydroxide or oxide.

24. The method according to any of the preceding claims, characterized in that the organometallic complex is dosed into the fuel at any stage in the fuel supply chain.

25. A method for regenerating a particulate filter trap, the method comprises adding to a fuel, before combustion thereof, a composition comprising an organometallic complex consisting essentially of a group I metal, characterized in that the concentration of the complex metal organometallic in the fuel, before combustion, is 100 ppm or less, and wherein the organometallic complex comprises an alkali metal salt of a succinic acid substituted with alkyl or alkenyl.

26. The method according to claim 25, characterized in that the metal concentration of the organometallic complex in the fuel, before combustion, is 30 ppm or less.

27. The method according to claim 25 or claim 26, characterized in that the filter trap is a monolith type ceramic trap and the metal concentration of the organometallic complex of the fuel before combustion is 30 ppm or less.

28. The method according to claim 25 or claim 26, characterized in that the filter trap is a deep-bed trap and the metal concentration of the organometallic complex in the fuel, before combustion, is 30 ppm or less.

29. The method according to any of claims 25 to 28, characterized in that the organometallic complex comprises a complex of Na and / or K.

30. The method according to any of claims 25 to 29, characterized in that the organometallic complex is soluble in fuel.

31. The method according to any of claims 25 to 30, characterized in that the complex Organometallic is classified to fuel at any stage in the fuel supply chain.

32. A process for improving the oxidation of carbonaceous products derived from combustion or fuel pyrolysis, the process comprises adding to the fuel, before combustion thereof, a composition comprising an organometallic complex consisting essentially of a metal of group I or Group II, characterized in that the metal concentration of group I or group II of the organometallic complex in the fuel, before combustion, is 100 ppm or less, and in which the organometallic complex comprises an alkali metal or alkaline earth metal salt of a succinic acid substituted with alkyl or alkenyl.

33. The process according to claim 32, characterized in that the concentration of the metal of group I or group II of the organometallic complex in the fuel before combustion is 30 ppm or less.

34. The process according to claim 32 or claim 33, characterized in that it additionally comprises the use of a trap of particulate filter to collect particulates produced during combustion.

35. The process according to claim 34, characterized in that the filter trap is a monolith type ceramic trap and the metal concentration of group I or group II in the organometallic complex in the fuel, before combustion, is 30 ppm or less.

36. The process according to claim 34, characterized in that the filter trap is a deep-bed trap and the metal concentration of the organometallic complex of group I or group II in the fuel, before combustion, is 30 ppm or minor.

37. The process according to any of claims 32 to 36, characterized in that the organometallic complex of group I comprises a complex of Na and / or K.

38. The process according to any of claims 32 to 36, characterized in that the The organometallic complex of group II comprises a complex of Sr and / or Ca.

39. The process according to any of claims 32 to 38, characterized in that the organometallic complex is soluble in fuel.

40. The process according to any of claims 32 to 39, characterized in that the organometallic complex is dosed to the fuel at any stage in the fuel supply chain.

41. The use of a composition according to any of claims 32 to 40, characterized in that it is used as an additive for fuel, to improve the oxidation of carbonaceous products derived from combustion or fuel pyrolysis. RE ?? flMF-rc PP THE INVENTION A process for improving the oxidation of carbonaceous products derived from the combustion of fuel and / or the improvement of fuel combustion is described. The process comprises adding to the fuel, before combustion thereof, a composition comprising at least one organometallic complex of a metal of group I or at least one organometallic complex of a metal of group II, or a mixture thereof , characterized in that the metal concentration of the organometallic complex of group I or group II in the fuel before combustion is 30 ppm or less. The organometallic complex induces an acceptable spontaneous trap regeneration according to the test protocol presented in the examples.