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INVENTION
Russian Federation Patent RU2296152

METHOD FOR IMPROVING THE WORK OF BURNING DIESEL

Name of the inventor: Gregory H. Ginter (US); Devlin, Mark T. (US); RUS Joseph W. (US); HUMAN David M. (US)
The name of the patentee: Afton Chemical Corp. (US)
Address for correspondence: 129010, Moscow, ul. Boris Spassky, 25, p.3, Ltd. "Gorodissky and Partners", pat.pov. S.A.Dorofeevu
Starting date of the patent: 2004.10.01

The present invention relates to the use of a fuel additive for protecting the combustion systems of diesel engines and to improve their performance. The method is to improve at least one of the following parameters in the diesel fuel combustion system: engine durability, fuel economy and film formation at the interface with the engine lubricating oil. The method comprises supplying diesel fuel containing additive with a compound of manganese in the combustion chamber of the diesel fuel in the combustion system diesel fuel combustion in the combustion chamber to produce at least one byproduct comprising the compound of manganese, supplying a compound containing manganese in an amount sufficient to form a complex compound with at least one byproduct of combustion, with a compound containing manganese comprises from about 5 to 30 mg Mn / liter fuel. In this machine oil comprises at least 3% by weight. soot. combustion of Diesel fuel is comprised of one or more components: exhaust gas recirculation systems, hot or chilled, turbocharger with variable spiral or turbocharger of variable geometry, fuel injection system with a common rail, electronically controlled block injectors with hydraulically turbonagnetaemye and postohlazhdaemye-fuel system systems with increased mean pressure during fuel injection and with high speed injection system of electronic control fuel mixture, fuel and exhaust byproducts of the engine system with a variable drive valve system with uniform compression upon ignition, and coating with a low coefficient of friction on the surfaces motor. diesel fuel combustion system operation is enhanced by improving the quality of lubricating oil containing soot as a byproduct of combustion.

DESCRIPTION OF THE INVENTION

The present invention relates to the use of a fuel additive for protecting the combustion systems of diesel fuel and improve their performance. The additive contains one or more manganese compounds. The additive may be introduced into the combustion chamber as part of the fuel. The additive improves the performance of combustion systems of diesel fuel due to, for example, improve the durability of the engine, the service life of lubricants and fuel economy.

It is well known in the automobile industry, or any industry where hydrocarbonaceous fuels used, and the desire to reduce the amount of gases emitted during combustion of fuel, using different strategies. For example, the most common way to reduce during the combustion exhaust gases from the engine with spark plugs is the careful management of the content of the fuel mixture and its ignition time. Delayed ignition timing at the most efficient ratio between fuel and air in the mixture reduces the emission of oxides of nitrogen and hydrocarbons into the atmosphere and the excess delay time of ignition increases the output of the carbon monoxide and hydrocarbon. Increasing engine speed reduces hydrocarbon output, but the amount of nitrogen oxides produced increases with increasing load. Increasing coolant temperature reduces hydrocarbon emissions but increases NOx output.

Diesel system put forward a number of problems related to the management of the waste gases. Reduction Strategies dispersed and gaseous hydrocarbon emissions include optimizing fuel injection and air motion, effective fuel atomization at varying loads, the time of fuel injection control, minimization of parasitic losses in combustion chambers, low volume chamber or nozzles in the valve cover for direct injection, reducing the flow lubricating oil and the rapid heating of the engine.

New diesel fuel combustion systems have been developed in order to improve their various performance and have been used with some new technologies, which may include one or more technologies from among such as improved turbochargers, fuel injection device, an electronic engine control, coatings with low friction coefficient on the surfaces of the engine and means for recycling the flue gases. Many of these devices and systems, in turn, lead to new requirements for the operation of the engine and to find a compromise between these requirements. For example, the use of systems for recycling flue gases leads to increased amounts of by-products of combustion, which means increased soot in oils used in engines. In other words, a trade-off when using the exhaust gas recirculation systems may be that the lubricating oils for diesel engines can be expected higher soot content. Other types of technology and lead to a relatively high content of carbon black in the diesel engine lubricating oils.

Additives used in the methods described herein are inorganic or organometallic compounds containing manganese and soluble in fuels. This fuel is then combusted in a diesel fuel combustion system to form products of combustion, and comprising a manganese compound.

A method for improving operation of diesel fuel combustion system is supplying a diesel fuel comprising an additive in the form of manganese compounds in a diesel fuel combustion chamber; burning fuel in the combustor to form at least one by-product of combustion containing compound with manganese, is added in an amount effective to produce a complex compound with at least one side combustion product, the system burning diesel fuel contains lubricant oil by at least 3 wt.% soot, and its performance improved.

For combustion systems on diesel fuel, whose work is improved by using the present invention include all combustion engines running on diesel fuel. Under combustion systems herein refers to any and all internal and external combustion devices, machines, engines, turbines, boilers, incinerators, boilers evaporation, stationary combustion chamber, and the like which can combust and in which can be burned diesel fuel. In one example, the diesel fuel combustion system requires the use of engine oil whose composition allows it to be at least 3 wt.% Soot. (Composition of oils for engines with high load, according to standard API CH-4 must prevent wear of the engine when the content of carbon black of at least 3 wt.%). In another example, the lubricating oil composition must provide a carbon black content of at least about 5 wt.%.

Diesel fuel combustion systems are using one or more new components which may result in increased soot levels in lubricating oils for engines. These new components may require an increase in the wear resistance of engines and increase the performance of lubricating oils. Such components for diesel fuel combustion systems include (but are not limited to): the exhaust gas recirculation system (hot or refrigerated), turbochargers with variable spiral / turbochargers with variable geometry fuel injection device with a common rail, unit injectors with hydraulic and electronic control systems for turbonagnetaniya air after cooling to increase medium-pressure device of the injected fuel and the fuel injection rate, electronic air supply control system and the fuel in the combustion chamber and the flue gas, the device with a variable drive for valves, uniform compression system and ignition of the injected fuel and coatings with low friction (for example, carbon-based and PTFE) on engine surfaces.

Each of these new components for diesel fuel combustion system particularly enhances the efficiency and performance of the entire system. Among several compromises caused by their use, can be called increase soot in lubricating oils and improving engine performance engine oils to improve durability (new technology to reduce engine wear).

By "diesel fuel" herein is meant one or more fuels selected from the group consisting of diesel fuel, biodiesel, biodizelproizvodnogo fuel, synthetic diesel, diesel fuel treated with oxidizing agents for the control of dispersed components and mixtures thereof, and other products, relevant definitions ASTM D975 standard. In one example, the sulfur content in diesel fuels should be less than 100 ppm (parts per million), and in another example, the sulfur content should be less than 30 ppm.

Metal referred to herein is elemental manganese and manganese ion consumables with the element and mixtures of compounds containing manganese. Such compounds containing manganese, may be inorganic or organic. economically and efficiently produce, secrete or produce manganese or manganese ions in their place of use.

Inorganic compounds containing manganese in this invention may be, without limitation, for example, fluorides, chlorides, bromides, iodides, oxides, nitrates, sulfates, phosphates, nitrides, hydrides, hydroxides, carbonates, and mixtures thereof. Manganese sulfates and phosphates can be used efficiently, and in some installations for fuels and burning them can prevent by-products of combustion additional presence of sulfur and phosphorus. Organometallic compounds include manganese compounds with alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, ethers, naphthanates, carboxylic acids, amides, acetylacetonates and their mixtures as a part ligandovyh systems.

In one example, organometallic compounds containing Mn include manganese compounds such as tricarbonyl. Such compounds are available in US Patents №№ 4568357, 4674447, 5113803, 5599357, 5944858 and European Patent № 466512B1

Suitable compounds of type manganese tricarbonyl, which can be used include cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl tricarbonyl manganese, tert-butylcyclopentadienyl manganese tricarbonyl, tricarbonyl oktiltsiklopentadienil manganese tricarbonyl dodetsiklopentadienil manganese etilmetiltsiklopentadienil manganese tricarbonyl, indenyl manganese tricarbonyl, and the like, including mixtures of two or more thereof. In one example shown cyclopentadienyls trikarbonily manganese, which are liquid at room temperature such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, liquid mixtures of cyclopentadienyl manganese tricarbonyl and methylcyclopentadienyl manganese tricarbonyl, mixtures of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl, etc.

Preparation of such compounds is described in the literature, for example, in U.S. Patent № 2818417, on which data is completely specified.

When comprise additives for use in the methods and systems of the present invention, compounds containing manganese, used in amounts sufficient to improve the performance of diesel fuel combustion systems like those described herein. The amount or concentration of the additive may be selected based on specific components introduced at a specific combustion system and, based on how those components affect, for example, the amount of soot in the lubricating oil emerging used for operation of the combustion system. The amount or concentration of the additive may be selected based on the concentration of sulfur in diesel fuel. Exemplary manganese compound processing speed can exceed 100 mg / l, up to 50 mg / l, and in one example, be from 5 to 30 mg / l.

soot disclosed herein reduces the total weight of the formed soot. In addition, however, this additive enhances the quality of the soot particles, at least with regard to their effect on diesel engine lubricating oils. Additives containing manganese, reduce the magnitude of the relationship between the elemental carbon (EC) and the soluble organic fraction (SOF). This ratio EC to SOF is believed to affect the hardness of soot particles and thereby the film strength. Reducing the ratio EC to SOF, apparently improves quality grease containing soot. Effect of soot properties on the formation of films at the interface and thereby the lubrication ability, containing carbon black, to prevent wear has been described in SAE 2002-01-2793 (Devlin et al, "Film formation Properties of Polymers in the Presence of Abrasive Contaminants") . In this article, the wear of diesel engines operating at high load levels, correlated with the formation of the films at the interface, the presence of which are determined by means of high frequency interference unit (VCHVU).

Additive described herein improves soot particle quality as showing measurement of film thickness on the interface of the first comparative study. Lubricating oils containing different amounts of soot were tested Using VCHVU formed using a manganese-containing additive, and without this additives. The processing speed of manganese-containing additive in these tests was 10 mg-Mn / liter. The following results were obtained:

1. These fluids were examined in connection with the fact that the additives therein are selected such that the film formed at the interface (cm. 2003-01-2793). The higher the test result the better the ability to form a film of liquid at the interface in the presence of carbon black.

2. See. US Patent number 5,075,383.

3. See. US Patent number 6,107,257.

In a second comparative test, lubricating oils containing equal amounts of soot but with different processing speeds manganese-containing additive were tested by VCHVU. The ash content was 6 wt.% in the test samples.

1. These fluids were investigated in connection with the fact that the additives therein are selected such that the film formed at the interface (cm. 2003-01-2793). The higher the test result the better the ability to form a film of liquid at the interface in the presence of carbon black.

2. See. US Patent number 5,075,383.

3. See. US Patent number 6,107,257.

As can be seen from the tables, the film thickness is increased in every case when the MMT additive was used. Therefore, the work on diesel engines with additive improves with lower fuel consumption, lower friction (enhanced wear resistance) and improving the life of lubricating oils (lengthens the time between oil changes).

The term "complex" or "complexing" is used herein to describe the combination of or the reaction of a compound containing manganese byproducts from the combustion of fuel, such as toxic substances, soot and other particulates. The combination contains ionic or covalent reaction or other communications connection to a metal byproduct of combustion. The term "by-product of combustion" and represents, but not limited to, particulates, soot, unburned soot, uncombusted hydrocarbons, partially combusted hydrocarbons, combusted hydrocarbons, oxides of nitrogen and sulfur, and any other gas, vapor, particle or compound that are formed by combustion.

and reference is made to the term "improved" in the context of a diesel fuel combustion systems. The term "enhanced" means an improvement in the diesel fuel combustion system in relation to the work of a similar system in which the fuel is not burned with a manganese compound. Improved work includes, but is not limited to an increase in the service life of lubricating oils for diesel engines and reduced engine wear and fuel consumption.

Note that the reactants and components referred to in the description or in the claims, their chemical names in the singular or plural, are identified as existing before coming into contact with another substance referred to by chemical name or chemical type (e.g., base fuel, solvent, and etc.). It is important not what chemical changes, transformations and / or reactions take place in the resulting mixture or solution or reaction medium, and that these changes, transformations and / or reactions are the natural result of bringing together the specified reactants and / or components under conditions disclosed herein. Thus the reactants and components are identified as ingredients, or joined together for a given chemical reaction (for example, to obtain the organometallic compound) or to form a desired composition (such as an additive concentrate or an additive mixture of fuel). and it is believed that the additive components can be added to base fuels or admixed thereto individually and / or as components, they can be used in the preparation of preformed additive combinations and / or subcombinations. Therefore, even if the claims may refer to substances, components and / or ingredients in the present tense ( "comprises", "it is", etc.), but the substance, component or ingredient called as it is called directly before the first time it is mixed with one or more other substances, components and / or ingredients in accordance with the present disclosure. The fact that a substance, component or ingredient may have lost its original state due to a chemical reaction or transformation as a result of mixing operations or immediately thereafter is thus has no value for the accurate understanding and appreciation of this disclosure and the claims.

In many places in the specification makes reference to a number of US patents, published foreign applications at about inventions and published technical articles. All these documents are incorporated into this description.

The invention can in practice be significantly changed. Therefore the foregoing description is not intended to limit, and should not be construed as limiting the invention to the specific examples given above. That is subject to coverage, it is contained in the claims and their equivalents are permitted by law.

CLAIM

1. A method for improving at least one of the following parameters in the diesel fuel combustion system: engine durability, fuel economy and film formation at the interface with the engine lubricating oil comprising supplying diesel fuel containing additive with a manganese compound, a diesel fuel combustion chamber a diesel fuel combustion system, the combustion of fuel in the combustion chamber to produce at least one byproduct comprising the manganese compound; wherein the compound containing manganese comprises from about 5 to 30 mg Mn / liter fuel, wherein the lubricating oil comprises at least 3 wt% carbon black, wherein the firing system of the diesel fuel consists of one or more components:. System recirculated flue gases, hot or chilled, turbocharger with variable spiral or turbocharger of variable geometry, fuel injection system with a common rail, electronically controlled block injectors with hydraulically turbonagnetaemye and postohlazhdaemye fuel-air systems, with an increased mean pressure during fuel injection and increased injection speed, the electronic control fuel mixture, fuel and exhaust byproducts in the motor drive system with variable valve system with homogeneous compression ignition, and when the coating with a low coefficient of friction on the surfaces of the engine, thereby improving operation of diesel fuel combustion systems.

2. The method of claim 1, wherein the diesel fuel is selected from the group consisting of diesel fuel, biodiesel fuel derived from biodiesel, synthetic diesel and mixtures thereof.

3. The method of claim 1, wherein the diesel fuel contains less than about 30 ppm sulfur.

4. The method of claim 1, wherein the compound containing manganese is manganese inorganic compound.

5. The method of claim 4, wherein 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 of claim 1, wherein the compound containing manganese is an organometallic compound.

7. The method of claim 6, wherein the organometallic compound is selected from the group consisting of alcohols, aldehydes, ketones, esters, anhydrides, sulfonates, phosphonates, chelates, phenates, ethers, naphthenates, carboxylic acids, amides, acetyl acetonates and mixtures.

8. The method of claim 6, wherein the organometallic compound comprises methylcyclopentadienyl manganese tricarbonyl.

9. The method of claim 1, wherein the compound containing manganese is selected from the following group: cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl tricarbonyl manganese, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tert-butylcyclopentadienyl manganese tricarbonyl, tricarbonyl oktiltsiklopentadienil manganese tricarbonyl dodetsiklopentadienil manganese etilmetiltsiklopentadienil manganese tricarbonyl, indenyl manganese tricarbonyl, and the like, including mixtures of two or more thereof.

10. The method of claim 1, wherein the combustion byproduct is selected from the group consisting of particulate matter, soot, unburned soot, uncombusted hydrocarbons, partially burned hydrocarbons, unburned hydrocarbons, nitrogen oxides and sulfur.

11. The method of claim 1, wherein the engine oil is formulated to prevent wear at a content therein, at least 3 wt.% Of carbon black as determined according to the API CH-4 standard in the test engine.

12. The method of claim 1, wherein the engine oil contains at least 6 wt.% Carbon black.

print version
Publication date 07.04.2007gg

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