EP1917332B1 - Verwendung von schmiermitteln - Google Patents

Verwendung von schmiermitteln Download PDF

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Publication number
EP1917332B1
EP1917332B1 EP06777023.0A EP06777023A EP1917332B1 EP 1917332 B1 EP1917332 B1 EP 1917332B1 EP 06777023 A EP06777023 A EP 06777023A EP 1917332 B1 EP1917332 B1 EP 1917332B1
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Prior art keywords
engine
ppm
oil
combustion
ions
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English (en)
French (fr)
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EP1917332A1 (de
Inventor
Bo Kylberg
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Statoil Fuel & Retail Lubricants Sweden AB
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Statoil Fuel & Retail Lubricants Sweden AB
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/10—Groups 5 or 15
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/50—Emission or smoke controlling properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

Definitions

  • This invention relates to engine lubricant oils, in particular diesel engine lubricant oils, which are formed using at least two combustion enhancers which contain different metal ions.
  • the combustion enhancers contain cerium ions and iron ions respectively.
  • NOx oxides of nitrogen
  • SOx and sulphur salts sulphur salts
  • US 2004/0261313 describes a fuel comprising an iron and/or a cerium compound which is used in connection with a gel.
  • US 4474580 describes the use of a mixture of iron enolate and cerium enolate as a additive for fuel.
  • US 4568360 describes further fuel additive compositions formed from mixed organometallic compositions, compositions comprising cerium and iron complexes are disclosed.
  • US 6096104 describes a mixture of at least three different metal compounds as fuel additives.
  • US 2005/0160663 describes a cleaner burning diesel fuel employing a fuel borne metal catalyst.
  • FR-A1-2 804 102 discloses a composition comprising a cerium compound and a second metallic compound selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr.
  • the composition may be used as a lubricant.
  • One of the uses is to prevent oxidation of siloxane lubricating oils.
  • US 2004/031192 A1 discloses a fuel composition comprising cerium alkylbenzene sulphonate, iron thallate and calcium alkylbenzene sulphonate. The use is as fuel additives.
  • US 2004/194454 A1 discloses diesel engine lubricating oil compositions comprising organo-metallic compounds. The problem with adding these materials to fuels is that vehicles use a lot of fuel. Even at very low concentrations therefore, vehicles are still using very significant amounts of the additive to the fuel.
  • the present inventors have surprisingly realised that emissions reduction and numerous other benefits can be achieved by adding certain combustion enhancers to the engine lubricant oil as opposed to fuel. Since engines use much less lubricant oil than fuel, the amounts of additive which a vehicle uses are massively reduced. Moreover, the addition of the combustion enhancing package of the invention has been found to improve emissions in older vehicles making it ideal for use in the developing world.
  • a lubricant oil comprising a particular mixture of combustion enhancers has the ability not only to reduce emissions but also to clean the engine in a vehicle.
  • the invention provides use in a combustion engine of a first combustion enhancer which is a cerium alkylbenzene sulphonate, wherein Ce ions are present in a concentration of from 0.1 to 1000 ppm, and a second combustion enhancer which is an iron alkyl carboxylate, wherein Fe ions are present in a concentration of from 0.1 to 2000 ppm, in a synthetic or mineral lubricant oil.
  • a first combustion enhancer which is a cerium alkylbenzene sulphonate, wherein Ce ions are present in a concentration of from 0.1 to 1000 ppm
  • a second combustion enhancer which is an iron alkyl carboxylate, wherein Fe ions are present in a concentration of from 0.1 to 2000 ppm, in a synthetic or mineral lubricant oil.
  • the Ce ions are present in a concentration of from 1 to 20 ppm.
  • Fe ions are present in a concentration of from 1 to 200 ppm.
  • the invention provides use as stated above for reducing the emissions of said engine, in particular smoke emissions.
  • the invention provides use as stated above for reducing the smoke emissions from said engine by at least 5 %.
  • the invention provides use according to the above for cleaning said engine, e.g. removing carbonaceous deposits from said engine.
  • the invention provides use according to the above for increasing the service life of a vehicle comprising said engine.
  • the invention provides use as stated above for reducing lubricant oil consumption in said engine.
  • the invention provides use of a synthetic or mineral lubricant oil comprising at least two combustion enhancers to both clean a combustion engine and reduce emissions from said engine wherein the first combustion enhancer is a cerium alkylbenzene sulphonate wherein Ce ions are present in a concentration of from 0.1 to 1000 ppm and the second combustion enhancer is an iron alkyl carboxylate wherein Fe ions are present in a concentration of from 0.1 to 2000 ppm.
  • the first combustion enhancer is a cerium alkylbenzene sulphonate wherein Ce ions are present in a concentration of from 0.1 to 1000 ppm
  • the second combustion enhancer is an iron alkyl carboxylate wherein Fe ions are present in a concentration of from 0.1 to 2000 ppm.
  • the invention provides use according to the above, wherein the combustion enhancers are present in the lubricant oil added to a vechicle and not in a fuel added to the vehicle.
  • lubricant oil embraces any lubricant oil useful in a combustion engine such as a four-stroke or two-stroke engine, especially a diesel engine.
  • the lubricant oil may be a synthetic or a mineral lubricant such as mineral HDDO (Heavy Duty Diesel Oil).
  • the actual nature of the motor oil used is not itself critical.
  • Engine oils are typically formed from a vacuum gas oil fraction of crude oil.
  • a suitable oil for use in this invention is Statoil's PowerWay 15W-40.
  • reducing emissions from an engine is meant that at least one of the undesirable components of the engine exhaust is reduced relative to an engine operating in the absence of a lubricant oil containing the additives of the invention (i.e. one operating with the lubricant oil but no additives).
  • a lubricant oil containing the additives of the invention i.e. one operating with the lubricant oil but no additives.
  • the NOx, particulates and/or smoke emitted by the engine during operation is reduced relative to an engine operating in the absence of a lubricant containing the additives oil of the invention.
  • the lubricant oil with the combustion enhancing additives of the invention reduces smoke emissions from an engine.
  • cleaning the engine is meant that carbonaceous deposits which form during engine operation, e.g. on the valve covers or crankcase, are prevented, reduced or eliminated relative to an engine operating in the absence of a lubricating oil with the additives of the invention (i.e. one operating with the lubricant oil but no additives).
  • increasing the service life of an engine/vehicle is meant that the distance travelled by a vehicle, or the number of hours of operation of the vehicle, between services is increased relative to an engine operating in the absence of a lubricating oil of the invention (i.e. one operating with the lubricant oil but no additives).
  • reducing lubricant oil consumption is meant that an engine using the lubricant oil of the invention uses less lubricant oil than one operating in the absence of a lubricating oil of the invention (i.e. one operating with the lubricant oil but no additives).
  • Ce can take the 3 + or 4 + oxidation state. It is also highly preferable that the metal ion is present in the combustion enhancer in a form which is readily soluble or dispersible in the lubricant oil. The metal ions may therefore be in a molecular or particulate form which is soluble or dispersible in lubrication oil.
  • the first combustion enhancer is a cerium alkylbenzene sulphonate.
  • the first combustion enhancer operates most effectively within the cylinder area of an engine.
  • the second combustion enhancer comprises iron ions, especially Fe 2+ ions.
  • the second combustion enhancer is in a form which is soluble or dispersible in the lubricant oil
  • the second combustion enhancer is an iron alkylcarboxylate. It has been surprisingly found that the second combustion enhancer operates most effectively within the crankcase ventilation system of an engine.
  • Suitable additives containing, for example, cerium ions or iron irons are available commercially from suppliers.
  • the combustion-enhancing additives of use in the lubricant oil act as pro-catalysts.
  • the combustion enhancers When the engine is in operation, the combustion enhancers combust at the intended site, e.g. in the crankcase ventilation chamber or the cylinders of the engine, generating the active catalyst.
  • the active catalyst is thus typically a metal, iron or cerium, oxide, Fe 2 O 3 , CeO 2 Ce 2 O 3 . This could be in molecular, nano-particulate, particulate or in any other form of aggregated metal oxide.
  • the catalyst generated from the combustion enhancing additives of the invention is nanoparticulate, e.g. less than 500 nm in particle size, especially less than 250 nm in particle size.
  • the reaction catalysed by the metal oxide is the formation of carbon dioxide (CO 2 ) and/or carbon monoxide (CO) by the catalyst-assisted combustion of heavy hydrocarbon and/or coke residues originating from incompletely combusted fuel and/ or lubricant base oil, thus eliminating all forms of carbon-based or carbon-containing smoke-generating particles, aggregates, aerosols etc.
  • CO 2 carbon dioxide
  • CO carbon monoxide
  • the weight ratio of the combustion enhancers to each other may vary from 1:1000 to 1000:1 by weight, preferably 1:100 to 100:1, more preferably 1:50 to 50:1, especially 1:25 to 25:1, most especially 1:10 to 10:1. It is preferred if the second combustion enhancer is present in excess compared to the first combustion enhancer.
  • the most preferred weight ratios are therefore first enhancer: second enhancer 1:100 to 1:1, preferably 1:50 to 1:5, more preferably 1:25, to 1:8, e.g. 1:10.
  • the amount of each combustion enhancer employed (in weight terms) in the lubricant oil may be in the range 1 to 1000 ppm, preferably 1 to 100 ppm with respect to the metal ion in question.
  • a lubricant wherein the first combustion enhancer, preferably operating from the cylinder area of an engine, is present in a concentration of from 0.1 to 1000 ppm, preferably from 1 to 100 ppm, more preferably 2 to 50, most preferably from 5 to 12 ppm with respect to the metal ion in question.
  • the second combustion enhancer ideally operating from the crankcase ventilation of an engine, is present in a concentration of from 0.1 to 2000 ppm, preferably from 1 to 1000 ppm, more preferably from 2 to 200 ppm, especially 5 to 150 ppm, most especially from 10 to 120 ppm with respect to the metal ion in question.
  • the lubricant oil of the invention may contain other standard lubrication oil additives in addition to the combustion enhancers herein described.
  • a lubricant oil additionally comprising a noise reduction agent, preferably a pour point depressant (PPD).
  • PPD is preferably a short chained poly(alkyl-methacrylate) (PAMA).
  • PAMA poly(alkyl-methacrylate)
  • Most preferably said PPD is added so that a relatively high concentration is obtained, e.g. 1 to 5 % approximately 3% by weight in the oil.
  • the invention provides the use of a pour point depressant as a noise reducing additive.
  • the fuel in the engine where the lubricant according to the invention may be used may be any fuel used for engines in vehicles, and may preferably be a liquid hydrocarbon fuel which may be a hydrocarbonaceous petroleum distillate fuel such as motor gasoline as defined by ASTM Specification D481 or diesel fuel or fuel oil as defined by ASTM Specification D975.
  • a liquid hydrocarbon fuel comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo- nitro compounds and the like (e.
  • liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale and coal.
  • hydrocarbon fuels which are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarbonaceous materials, are also included. Examples of such mixtures are combination of gasoline and ethanol, diesel fuel and ether, diesel fuel and methyl esters of vegetable or animal oils. Included are fuels known as gas-to-liquid fuels, GTL. The fuel may also be lead containing or lead free. The fuel may also be an emulsified fuel, either a macro- emulsion, a micro-emulsion or combinations thereof.
  • the lubricant oil of the invention can be used in conjunction with any internal combustion engine, e.g. four-stroke engines but also two-stroke engines, especially a diesel engine.
  • the vehicle may be a road or railroad vehicle, ship/boat or aircraft, especially a bus.
  • the lubricant oil of the invention is of particular utility with older engines, e.g. pre 2000 engines, preferably pre 1997 engines, more preferably pre 1995 engines, especially pre 1993 engines.
  • the engine is one which has done a large mileage, e.g. at least 75,000 km, preferably at least 100,000 km preferably at least 125,000 km.
  • a large mileage e.g. at least 75,000 km, preferably at least 100,000 km preferably at least 125,000 km.
  • Such engines are used in vehicles throughout the Developing World. It is especially preferred if the lubricant oil is employed in a large diesel engine vehicle such as a bus or lorry or an agricultural vehicle, or a railroad engine
  • the invention provides an engine comprising the lubricant oil of the invention.
  • the reduction in smoke emissions measured as described in example 7 using a smoke meter, can be at least 3%, e.g. at least 5 %, e.g. at least 10 %, preferably at least 20% relative to an engine run on an otherwise identical lubricant oil without the combustion enhancers of the invention.
  • the smoke eliminated by the invention may derive from the incomplete combustion of the oil itself or from the fuel. Reduction of smoke from fuel is particularly effective in engines using a closed crankcase ventilation system.
  • the additives of the present invention can reduce lubricant oil consumption by at least 3%, e.g. at least 5 %, e.g. at least 10 %, preferably at least 20% relative to an engine run on an otherwise identical lubricant oil without the combustion enhancers of the invention.
  • the additives of the present invention can increase service life of an engine by at least 3%, e.g. at least 5 %, e.g. at least 10 %, preferably at least 20% relative to an engine run on an otherwise identical lubricant oil without the combustion enhancers of the invention.
  • the additives of the present invention can reduce carbonaceous deposits within an engine, e.g. carbonaceous deposits on a cylinder by at least 3%, e.g. at least 5 %, e.g. at least 10 %, preferably at least 20% relative to an engine run on an otherwise identical lubricant oil without the combustion enhancers of the invention.
  • the additives of the present invention can increase the distance travelled by a vehicle between oil changes by at least 3%, e.g. at least 5 %, e.g. at least 10 %, preferably at least 20% relative to an engine run on an otherwise identical lubricant oil without the combustion enhancers of the invention.
  • the lubricant of the invention can be manufactured simply be adding the combustion enhancers of the invention in appropriate amounts to a motor oil.
  • the market is replete with appropriate motor oils such as PowerWay 15W-40 sold by Statoil.
  • the combustion enhancing additives prefferably be sold in a form ready for addition by the user to a standard motor oil, e.g. a diesel oil.
  • a standard motor oil e.g. a diesel oil.
  • the invention provides a kit comprising a source of cerium ions and a separate source of iron ions with instructions for how much of each to add to a fixed amount of motor oil, e.g. to achieve a concentration of 10 ppm Ce ions and 100 ppm Fe ions.
  • the bus dismantling company provided 3 buses which were ready for scrap having reclined Volvo motors.
  • a test method especially adapted for heating oil was used, with a minor modification.
  • the oil is burnt in a heating oil furnace (1) and samples taken from the exhaust thereof (2) using a True Spot smoke tester (3). 15 pump strokes were used for sampling, (see Figure 1 ).
  • the exhaust gas is drawn across a filter membrane by the pumping action. This filter is then checked for colour changes and/or the appearance of particles. Any particles found may be counted and sized by optical microscopy.
  • the test output is a pass/fail rating. Additives were added to the engine oil in different concentrations and the effect upon smoke generation was observed.
  • a third set of tests was performed on buses 1 and 2.
  • the buses were started and run warm by idling for approx. 40 minutes whereupon a first smoke sample was drawn from the exhaust pipe and at the same time a first dose was added with respective additive directly into the lubricant tank of the bus.
  • the additive was a premix of approx. 1 dl engine oil with cerium and iron additives (same components as in Example 1 and 2) giving a final concentration in the engine oil (approx 18 liter of oil in the engine) of 4 ppm cerium ions and 10 ppm Fe ions.
  • a second smoke sample was taken out in the same manner as above and a further dose of the same additive was added, resulting in a concentration in the engine oil of approx. 8 ppm cerium ions and 20 ppm iron ions.
  • the test was performed on a Lister Petter diesel engine, model 4X90, performing a running cycle simulating city bus traffic, for 536 h.
  • the engine was a new engine that had only about 100h running time before the test.
  • the test oil was the new oil claimed in the invention, in a formulation containing cerium alkylbenzene sulphonate (10 ppm cerium (III) ions) and iron (II) alkylcarboxylate (100 ppm iron ions) added to a standard motor oil PowerWay 15W-40..
  • the test oil was put into the crankcase.
  • the test fuel contained 440 ppm sulphur.
  • Example 4 Using the engine of Example 4, analysis of the exhaust gases was made by using a special instrument for emissions analysis provided by Boo Instrument AB in Nacka, Sweden, a so-called multi-instrument.
  • the test oil was identical to the oil utilized in Example 4, and was tested under the name "PowerWay Low Smoke” (abbreviated LS)
  • PowerWay Low Smoke 15W-40 The characteristics of PowerWay Low Smoke 15W-40 are given below, in Table 2.
  • PowerWay is a trademark owned by Statoil. In the test there was a concentration of 10 ppm of the cerium ions and 100 ppm of the iron ions in said PowerWay Low Smoke 15W-40. Table 2.
  • Products 1, 2, 3 and 4 correspond to an oil (PowerWay) with low smoke additives according to the present invention, in combination with two different diesel qualities containing 440 ppm sulphur (S) and 919 ppm sulphur, respectively.
  • the additives used in PowerWay were 10 ppm cerium ions as the alkylbenzene sulphonate, and 100 ppm iron ions as the alkylcarboxylate.
  • Products 5 and 6 represent standard HDDO oil without any additives of the invention. Table 3. Comparison of different products with regard to exhaust gas composition Product Directly produced effect (kW) Spec.
  • the lubricant oil of the invention was used in tests on Mosgortrans buses.
  • Mosgotrans Depot No. 5 bus reference 05178 had completed 135,600 km before the trial began.
  • the lubricant oil was changed for the oil of the Invention (PowerWay 15W-40 with 10 ppm cerium ions as the alkylbenzene sulphonate and 100 ppm iron ions as the alkyl carboxylate. After 8000 km the oil was changed due to defective injectors. After 33,000 km the state of engine was reviewed.
  • a cleaner engine means an engine that may use less fuel and one which has significantly lower emissions.
  • a clean engine means longer engine life, the use of fewer spare parts, less servicing and consequent reduction in servicing manpower. Due to the clean engine, lubricating oil actually needs to be changed less frequently than with conventional oils meaning less lubricant oil used and less labour for oil changing. Fewer oil changes means less down time for a vehicle and hence the possibility of maintaining a smaller fleet.
  • the bus was tested on a cradle dynamometer with 515 mm roller diameters at ambient temperature 22 °C.
  • the setting of dynamometer was done by simulating of an overloaded vehicle road conditions (using typical vehicle inertia and road load curve).
  • the steady state test was performed with the vehicle at 60 km/h for 10 minutes.
  • the transient test was done using a Braunschweig bus test cycle.
  • the transient Braunschweig vehicle cycle simulates realistic road load conditions as shown in Figure 32 .
  • the measurement of smoke was performed via direct sampling of the raw exhaust gas stream.
  • the measurement of CO, CO 2 HC, NO x , particle mass (PM), particle number and size distribution are carried out using a diluted sampling method.
  • the diluted sampling method is based on a full flow dilution system, i.e. the total exhaust is diluted using Constant Volume Sample (CVS) concept.
  • the total volume of the mixture of exhaust and dilution air is measured by a Critical Flow Venturi (CFV) system.
  • CVS Constant Volume Sample
  • Horiba Mexa 9000 series (9400D) was used for CO, HC, NO x and CO x analysis.
  • the fuel consumption was calculated using a carbon balance method.
  • AVL Smoke Meter 415S was used for smoke measurement.
  • the particle number and size-distribution measurements were carried using an Electrical Low-Pressure Impactor (ELPI) (Dekati).
  • ELPI Electrical Low-Pressure Impactor
  • Table 5 Measurement principles Emission component Measurement principle Total hydrocarbons (THC) HFID (heated flame ionization detector, 190°C) Carbon monoxide (CO) NDIR (Non-dispersive infrared analyzer) Nitrogen oxides (NO, NO x ) CLA (chemiluminescence) Carbon dioxide (CO 2 ) NDIR (Non-dispersive infrared analyzer) Fuel consumption (FC) Carbon balance of HC, CO and CO 2 Particulate emissions (PM) Gravimetric Particle number and size-distribution Impactor Smoke Reflectometer

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (10)

  1. Verwendung in einem Verbrennungsmotor von einem ersten Verbrennungsverbesserer, der ein Ceralkylbenzensulfonat ist, wobei Ce-Ionen in einer Konzentration von 0,1 bis 1000 ppm vorhanden sind, und einem zweiten Verbrennungsverbesserer, der ein Eisenalkylcarboxyl ist, wobei Fe-Ionen in einer Konzentration von 0,1 bis 2000 ppm in einem synthetischen oder mineralischen Schmieröl vorhanden sind.
  2. Verwendung nach Anspruch 1, wobei Ce-Ionen in einer Konzentration von 1 bis 20 ppm vorhanden sind.
  3. Verwendung nach Anspruch 1, wobei Fe-Ionen in einer Konzentration von 1 bis 200 ppm vorhanden sind.
  4. Verwendung nach Anspruch 1 zur Verringerung der Emissionen des Motors, insbesondere Rauchemissionen.
  5. Verwendung nach Anspruch 4 zur Verringerung der Rauchemissionen vom Motor um mindestens 5 %.
  6. Verwendung nach Anspruch 1 zur Reinigung des Motors, z.B. Entfernung von kohlenstoffhaltigen Ablagerungen vom Motor.
  7. Verwendung nach Anspruch 1 zur Erhöhung der Lebensdauer eines Fahrzeugs, das den Motor umfasst.
  8. Verwendung nach Anspruch 1 zur Verringerung des Schmierölverbrauchs im Motor.
  9. Verwendung eines synthetischen oder mineralischen Schmieröls umfassend mindestens zwei Verbrennungsverbesserer sowohl zur Reinigung eines Verbrennungsmotors als auch zur Verringerung von Emissionen vom Motor, wobei der erste Verbrennungsverbesserer ein Ceralkylbenzensulfonat ist, wobei Ce-Ionen in einer Konzentration von 0,1 bis 1000 ppm vorhanden sind, und der zweite Verbrennungsverbesserer ein Eisenalkylcarboxyl ist, wobei Fe-Ionen in einer Konzentration von 0,1 bis 2000 ppm vorhanden sind.
  10. Verwendung nach einem der vorgehenden Ansprüche, wobei die Verbrennungsverbesserer im Schmieröl, welches zum Fahrzeug zugegeben wird, und nicht in einem Kraftstoff, der zum Fahrzeug zugegeben wird, vorhanden sind.
EP06777023.0A 2005-08-25 2006-08-23 Verwendung von schmiermitteln Not-in-force EP1917332B1 (de)

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FR2537593B1 (fr) * 1982-12-10 1986-04-11 Raffinage Cie Francaise Compositions organometalliques mixtes comprenant des elements des groupes du fer et des lanthanides, procede de preparation et application desdites compositions comme additifs pour combustibles ou carburants
RU2034868C1 (ru) * 1992-11-16 1995-05-10 Всероссийский научно-исследовательский институт по переработке нефти Способ получения присадки к полиорганосилоксанам
FR2804102B1 (fr) * 2000-01-26 2002-08-16 Rhodia Terres Rares Dispersion colloidale aqueuse d'un compose de cerium et d'au moins un autre element choisi parmi les terres rares, des metaux de transition, l'aluminium, le gallium et le zirconium, procede de preparation et utilisation
IT1318868B1 (it) * 2000-08-03 2003-09-10 Cesare Pedrazzini Additivo per ridurre il particolato nelle emissioni derivanti dallacombustione di gasolio ed olio combustibile e composizione carburante

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EA018857B1 (ru) 2013-11-29
EA200800541A1 (ru) 2008-10-30
BRPI0614886A2 (pt) 2011-04-19
UA93382C2 (ru) 2011-02-10
WO2007022962A1 (en) 2007-03-01
EP1917332A1 (de) 2008-05-07

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