MXPA04009504A - Method of enhancing the operation of diesel fuel combustion systems - Google Patents

Abstract

A method of enhancing the operation of diesel fuel combustion systems in a combustion system includes supplying a fuel and additive that includes a manganese compound to a diesel fuel combustion system. The fuel is then combusted in the combustion chamber to produce at least one byproduct including the manganese compound. The manganese compound is supplied in an amount effective to complex with the combustion byproduct. The diesel fuel combustion system operation is enhanced by improving the attributes of lubricating oil loaded with the combustion byproduct soot particles.

Description

METHOD TO IMPROVE THE OPERATION OF DIESEL FUEL COMBUSTION SYSTEMS FIELD OF THE INVENTION The present invention relates to the use of a fuel additive to protect and improve the operation of diesel fuel combustion systems. The additive contains one or more manganese compounds. The additive can be introduced into a combustion chamber as part of the fuel. The additive will improve the operation of diesel fuel combustion systems by improving, for example, wear inhibition, lubricating oil life and fuel economy. BACKGROUND OF THE INVENTION It is well known in the automotive industry, or in any industry where hydrocarbonaceous fuels are burned, to reduce tailpipe emissions using various strategies. For example, the most common method for reducing emissions from spark ignition engines is by careful control of the air-fuel ratio and ignition timing. The retardation of the synchronization of the ignition of the best efficiency scenario reduces the emissions of HC and NOx, while an excess in the delay of the ignition increases the output of CO and HC. Increase the motor speed reduces REF .: 158640 the emissions of HC, but not the emissions of N0X that increase with the load. Increasing the refrigerant temperature tends to reduce HC emissions, but this results in an increase in N0X emissions. Diesel systems present an additional set of challenges for the control of emissions. Strategies to reduce particulate matter and HC include optimizing fuel injection and air movement, effective fuel atomization at variable loads, control of fuel injection timing, minimization of parasitic losses in fuel chambers, combustion, low cavity volume or valve cover orifice nozzles for direct injection, reduction of lubricating oil contributions and rapid engine warm-up. The new diesel fuel combustion systems have been and are being designed to improve various performance attributes. Some new types of technology that will be employed may include one or more of the following: improved turbochargers, fuel injection systems, electronic engine controls, low friction coatings on engine surfaces, and exhaust gas recirculation devices. Many of these systems in turn result in new performance requirements and disadvantages in the total operation of the engine. For example, exhaust gas recirculation (EGR) systems result in the escape of increased combustion byproducts, which means increased soot in engine oils. In other words, a disadvantage in the use of EGR systems is that diesel engine lubricants can be expected to have a relatively higher soot content. Other types of technology also result in the lubricating oils of diesel engines having a relatively high soot content. DETAILED DESCRIPTION OF THE INVENTION The additives used in the methods described herein are compounds containing inorganic or organometallic soluble solvents in fuels. This fuel is then burned in a diesel fuel combustion system to produce combustion by-products that include the manganese compound. A method for improving the operation of a diesel fuel combustion system comprises supplying a diesel fuel comprising an additive that includes a manganese-containing compound to a diesel fuel combustion chamber in a diesel fuel combustion system, burning the fuel in the combustion chamber to produce at least one by-product comprising the compound containing manganese, the manganese-containing compound being supplied in an effective amount to be grouped with at least one by-product of combustion, wherein the diesel fuel combustion system comprises a motor oil and at least 3% by mass of soot charge, whereby the performance of the diesel fuel combustion system is improved. The diesel fuel combustion systems that can benefit from the present invention include all combustion engines that burn diesel fuels. By "combustion system" is meant herein any and all internal and external combustion devices, machines, motors, turbine engines, burners, incinerators, evaporative burners, stationary burners and the like, which may burn or in the which can be burned a diesel fuel. In one example, the diesel fuel combustion system requires a motor oil formulated to receive at least 3% by mass of soot charge. (Oils for heavy duty engines formulated to meet the API CH-4 standard must prevent wear in the presence of at least 3% by mass of soot load). In another example, the motor oil is formulated to receive at least about 5% by mass of soot charge. Diesel fuel combustion systems are being designed to incorporate one or more new components that can result in the accumulation of new levels of high mass of soot load in lubricating oils for engines. The new components can also demand increased lubricant performance against engine wear. These components of diesel fuel combustion systems include, but are not limited to, the following: exhaust gas recirculation systems, either hot or cooled; Variable spiral turbochargers / variable geometry turbochargers; common rail fuel injection systems; electronically controlled and hydraulically activated unit injectors; turbocharged and cooled down combustion air systems; systems capable of setting the injection speed and high average fuel injection pressure; electronic engine control systems for combustion, fuel and exhaust air; variable valve drive systems; homogeneous load compression ignition systems and low friction coatings (for example based on carbon and PTFE) on engine surfaces. The new components for diesel fuel combustion systems each contribute their own unique way to the efficiencies and performance of the overall system. Several disadvantages resulting from its use may include increased soot loading in the engine lubricating oil and increased lubricant performance with respect to engine wear (and wear of new components). By "diesel fuel" is meant herein one or more fuels selected from the group consisting of diesel fuel, biodiesel, fuel derived from biodiesel, synthetic diesel, diesel fuel treated with oxygenates for the control of particulate materials, and mixtures of the same and other products that meet the definitions of ASTM D975. In one example, the sulfur content of the diesel fuel would be less than about 100 ppm, and in a further example, the sulfur content would be less than about 30 ppm. The metal described herein includes elemental and ionic manganese, precursors thereof and mixtures of metal compounds including manganese. The compounds containing manganese can be either inorganic or organic. The generation, release or production in itself of manganese or manganese ions is also effective. The inorganic manganese-containing compounds of the present invention may include, for example and without limitation, fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, nitrides, hydrides, hydroxides, carbonates and mixtures thereof. Sulphates and manganese phosphates will be operative and may, in certain fuels and combustion applications, not present additional and unacceptable sulfur and phosphorus combustion byproducts. Organometallic compounds include manganese compounds with alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, naphthatates, carboxylic acids, amides, acetylacetonates and mixtures thereof as part of the ligand systems . In one example, organometallic compounds containing manganese are manganese tricarbonyl compounds. These compounds are shown, for example, in the patents of E.U.A. Nos. 4,568,357; 4,674,447; 5,113,803; 5,599,357; 5,944,858 and in European Patent No. 466 512 Bl. Compounds tricarbonyl Suitable manganese can be used include tricarbonyl ciclopentadienilmanganeso, tricarbonyl metilciclopentadienilmanganeso, tricarbonyl dimetilciclopentadienilmanganeso, tricarbonyl trimetilciclopentadienilmanganeso, tricarbonyl tetrametilciclopentadienilmanganeso, tricarbonyl pentametilciclopentadienilmanganeso, tricarbonyl etilciclopentadienilmanganeso, tricarbonyl dietilciclopentadienilmanganeso, tricarbonyl propilciclopentadienilmanganeso, tricarbonyl isopropilciclopentadienilmanganeso , tert-butylcyclopentadienylmanganese tricarbonyl, octylcyclopentadienylmanganese tricarbonyl, dodecylcyclopentadienylmanganese tricarbonyl, ethylmethylcyclopentadienylmanganose tricarbonyl, indenylmanganese tricarbonyl and the like, including mixtures of two or more of these compounds. An example includes cyclopentadienyl manganese tricarbonyls which are liquid at room temperature such as methylcyclopentadienylmanganese tricarbonyl, tricarbonyl of ethylcyclopentadienylmanganese, liquid mixtures of tricarbonyl of cyclopentadienylmanganese and tricarbonyl of methylcyclopentadienylmanganese, mixtures of carbonyl of methylcyclopentadienyl and tricarbonyl of ethylcyclopentadienylmanganese, etc. The preparation of these compounds are described in the literature, for example, U.S. No. 2,818,417, the disclosure of which is hereby incorporated in its entirety. When formulating additives for use in the methods and systems of the present invention, the manganese-containing compounds are employed in sufficient amounts to improve the operation of diesel fuel combustion systems such as those described herein. The amount or concentration of the additive can be selected based on the specific components incorporated in the particular combustion system and on how those components affect, for example, the amount of soot that the components cause to be charged in the lubricating oil used in the operation of the combustion system. The amount or concentration of the additive can also be selected based on the concentration of sulfur in the diesel fuel. Exemplary treatment rates of the manganese compound can be from more than 100 mg manganese / liter to about 50 mg / liter, and in one example from about 5 to about 30 mg / liter. The additive described herein results in a reduced total mass of soot produced. However, in addition, the additive improves the quality of the soot particles, at least with respect to the effect of the soot particles in the lubricating oils for diesel engines. Manganese-containing additives reduce the proportion of elemental carbon (EC) in relation to the soluble organic fraction (SOF, for its acronym in English). It is believed that this ratio of EC to SOF affects the hardness of the soot particles, thereby affecting the strength of the film. Reducing the ratio of EC to SOF seems to improve the quality of the lubricant loaded with soot. The effects of soot properties on the formation of boundary films and this capacity of the soot-laden lubricant to prevent wear have been described in SAE 2002-01-2793 (Devlin et al., "Film Formation Properties of Polymers in the Presence of Abrasive Contaminants "). In this document wear on heavy duty diesel engines is correlated with the formation of boundary layer films, whose presence is detected using a High Frequency Reciprocating Motion Equipment (HFRR). The additive described herein improves the quality of the soot particles as evidenced by the measurement of the thickness of the boundary layer film in a first comparative study. Lubricating oils containing different amounts of soot generated with and without the manganese-containing additive (MMT) were tested on the HFRR. The treatment speed of the manganese-containing additive in these tests was 10 mg-Mn / liter. The results were the following: Table I Effect of soot on lubricant limit film forming properties (1) 1. These fluids were examined since the additives in these fluids are those that form boundary films (see 2003-01-2793). The higher the test result, the better the ability of the fluid to form a boundary film in the presence of soot. 2. See patent of E.U.A. 5,075,383. 3. See patent of E.U.A. 6,107,257.

In a second comparative test, lubricating oils containing equal amounts of soot but variable treatment rates of additive containing manqaneso were tested in the HFRR. The charge of soot in the test samples was 6% by mass. The results were the following: Table II Effect of soot formed by fuels containing different amounts of Mn on the properties of limit film formation of lubricants (1) 1. These fluids were examined since the additives in these fluids are those that form boundary films (see 2003-01-2793). The higher the test result the better the ability of the fluid to form a boundary film in the presence of soot. 2. See patent of E.U.A. 5,075,383. 3. See patent of E.U.A. 6,107,257. As can be seen in the tables, the film thickness was improved (higher) in each case when the MMT additive was used. Consequently, the operation of diesel fuel combustion engines using the fuel additive is improved with lower fuel consumption, lower friction (increased wear inhibition) and increased lubricating oil life (extended length of time between changes in fuel consumption). oil). The terms "complex" or "group" are intended to describe in the present the combination of, or the reaction by, the manganese-containing compound with the combustion by-products such as pollutants, soot and other particulate materials. The combination includes covalent or ionic reactions or any other bond of the metal shell with the by-product of combustion. In addition, the term "combustion by-product" includes, but is not limited to, particulate materials, soot, unburned soot, unburnt hydrocarbons, partially burned hydrocarbons, burned hydrocarbons, nitrogen and sulfur oxides, and any other gas, vapor, particle or compound that results from the combustion of a fuel.

Reference is also made throughout the text to the term "improved" in the context of the operation of diesel fuel combustion systems. The term "improved" means an improvement in the operation of the diesel fuel combustion system in connection with the operation of a similar system that does not have a manganese compound burned therein. An "increased" operation includes, but is not limited to, a life of lubricating oil for increased diesel engines and reduced wear and fuel consumption of the engine. It should be understood that the reagents and components mentioned by their chemical name in any place in the description or claims thereof, whether they are mentioned in singular or plural, are identified as existing before coming into contact with another substance mentioned by their name. chemical name or chemical type (for example, base fuel, solvent, etc.). It does not matter what chemical changes, transformations and / or reactions, if any, take place in the resulting mixture or solution or reaction medium, since these changes, transformations and / or reactions are the natural result of putting the reagents and / or specified components together under the appropriate conditions according to this description. In this way, reagents and components are identified as ingredients that will be put together either by carrying out a desired chemical reaction (such as the formation of the organometallic compound) or by forming a desired composition (such as an additive concentrate or mixture). of fuels with additive). It should also be recognized that the additive components can be added or mixed in or with the base fuels individually per se and / or as components used to form combinations and / or subcombinations of preformed additives. In consecuense, even though the claims hereinafter may refer to substances, components and / or ingredients at the present time ("comprises", "is", etc.), the reference is to the substance, components or ingredients as they existed at the time just before they were combined or mixed with one or more other substances, components and / or ingredients according to the present disclosure. The fact that the substance, constituents or ingredient may have lost their original identity through a chemical reaction or transformation during the course of these combined or mixed operations or immediately after them is then completely indifferent to a precise understanding and appreciation of this description and the claims thereof. In numerous paragraphs throughout this description, reference has been made to several US patents, published foreign patent applications and published technical documents. All these cited documents are expressly incorporated in full in this description as if they were fully described herein. This invention is susceptible to considerable variations in its practice. Therefore, the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications set forth hereinbefore. Instead, what is intended to be covered is what is described in the following claims and the equivalents thereof that are allowed as a matter of law. The applicant does not intend to dedicate any described modality to the public, and to the extent that any of these modifications or alterations described may not fall literally within the scope of the claims, they are considered as part of the invention under the doctrine of equivalents. 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.

Claims (17)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A method for improving the operation of a diesel fuel combustion system, the method characterized in that it comprises: supplying a diesel fuel comprising an additive which includes a manganese-containing compound to a diesel fuel combustion chamber in a diesel fuel combustion system; burning the fuel in the combustion chamber to produce at least one by-product comprising the manganese-containing compound; the manganese-containing compound being supplied in an effective amount to be grouped with at least one combustion by-product, wherein the diesel fuel combustion system comprises an engine oil and at least 3% by mass of soot charge; whereby the performance of the diesel fuel combustion system is improved. The method according to claim 1, characterized in that the diesel fuel is selected from the group consisting of diesel fuel, biodiesel, fuel derived from biodiesel and synthetic diesel fuel, and mixtures thereof. 3. The method according to claim 1, characterized in that the diesel fuel contains less than about 30 ppm of sulfur. 4. The method according to claim 1, characterized in that the manganese-containing compound is an inorganic manganese compound. The method according to claim 4, characterized in that the inorganic manganese compound is selected from the group consisting of fluorides, chlorides', bromides, iodides, oxides, nitrates, sulfates, phosphates, nitrides, hydrides, hydroxides, carbonates and mixtures thereof. 6. The method according to claim 1, characterized in that the manganese-containing compound is an organometallic compound. The method according to claim 6, characterized in that the organometallic compound is selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, crown ethers, naphthatates, carboxylic acids, amides, acetylacetonates and mixtures thereof. The method according to claim 1, characterized in that the manganese-containing compound comprises about 5 to about 30 mgMn / liter of the fuel. 9. The method according to claim 6, characterized in that the organometallic compound comprises methylcyclopentadienylmanganese tricarbonyl. 10 The method according to claim 1, characterized in that the manganese-containing compound is selected from the following group: cyclopentadienylmanganese tricarbonyl, methylcyclopentadienylmanganose tricarbonyl, dimethyl-ilcyclopentadienylmanganese tricarbonyl, trimethylcyclopentadienylmanganese tricarbonyl, tetramethylcyclopentadienylmanganese tricarbonyl, pentametyl-cyclopentadienylmanganese tricarbonyl, tricarbonyl etilciclopentadienilmanganeso, tricarbonyl dietilciclopentadienilmanganeso, tricarbonyl propilciclopentadienilmanganeso, tricarbonyl isopropilciclopentadienilmanganeso, ricarbonilo tert-but ilciclopentadienilmanganeso, tricarbonyl ilciclopentadienilmanganeso October, tricarbonyl dodecilciclopentadienilmanganeso, tricarbonyl etilmetilciclopentadienilmanganeso, tricarbonyl indenilmanganeso and the like including mixtures of two or more of these compounds. eleven . The method according to claim 1, characterized in that the combustion by-product is selected from the group consisting of particulate materials, soot, unburned soot, unburnt hydrocarbons, partially burned hydrocarbons, burned hydrocarbons and nitrogen and sulfur oxides. The method according to claim 1, characterized in that the diesel fuel combustion system comprises one or more of the following components: exhaust gas recirculation systems, either hot or cooled; Variable spiral turbochargers / variable geometry turbochargers; common rail fuel injection systems; electronically controlled and hydraulically activated unit injectors; turbocharged and cooled down combustion air systems; systems capable of setting the injection speed and high average fuel injection pressure; electronic engine control systems for combustion, fuel and exhaust air; variable valve drive systems; homogeneous load compression ignition systems and low friction coatings on engine surfaces. 13. The method according to the claim 1, characterized in that the motor oil is formulated to receive at least 3% by mass of soot charge. The method according to claim 1, characterized in that the engine oil is formulated to prevent wear in the presence of at least 3% by mass of soot load, as categorized by engine tests API CH-4 15. The method according to claim 1, characterized in that the engine oil has at least 6% by mass of soot load. The method according to claim 1, characterized in that the operation of the diesel fuel combustion system is improved as compared to the operation of the same system without the additive that includes a manganese-containing compound. 17. A method for improving the operation of a diesel fuel combustion system, the method characterized in that it comprises: supplying a diesel fuel comprising an additive that includes a manganese-containing compound to a diesel fuel combustion chamber in a diesel fuel system; combustion of diesel fuel; burning the fuel in the combustion chamber to produce at least one by-product comprising the manganese-containing compound; the manganese-containing compound being supplied in an effective amount to be grouped with at least one combustion byproduct, wherein the diesel fuel combustion system comprises one or more of the following components: exhaust gas recirculation systems, either hot or chilled; Variable spiral turbochargers / variable geometry turbochargers; common rail fuel injection systems; electronically controlled and hydraulically activated unit injectors; turbocharged and cooled down combustion air systems; systems capable of setting the injection speed and high average fuel injection pressure; electronic engine control systems for combustion, fuel and exhaust air; variable valve drive systems; homogeneous load compression ignition systems and low friction coatings on engine surfaces. whereby the performance of the diesel fuel combustion system is improved.