WO2004094576A2 - Composition d'huile lubrifiante reduisant les depots de vernis et methode d'utilisation de cette composition - Google Patents

Composition d'huile lubrifiante reduisant les depots de vernis et methode d'utilisation de cette composition Download PDF

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WO2004094576A2
WO2004094576A2 PCT/US2004/010221 US2004010221W WO2004094576A2 WO 2004094576 A2 WO2004094576 A2 WO 2004094576A2 US 2004010221 W US2004010221 W US 2004010221W WO 2004094576 A2 WO2004094576 A2 WO 2004094576A2
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composition
group
concentration
oil
earth metal
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PCT/US2004/010221
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WO2004094576A3 (fr
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Exxonmobil Research And Engineering Company
Wells, Paul, Patrick
Carey, Vincent, Mark
Kelly, Kevin, John
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Priority to EP04759791A priority Critical patent/EP1615986A2/fr
Priority to CA002519539A priority patent/CA2519539A1/fr
Publication of WO2004094576A2 publication Critical patent/WO2004094576A2/fr
Publication of WO2004094576A3 publication Critical patent/WO2004094576A3/fr

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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • This invention relates to lubricating oil compositions that have surprisingly been shown to reduce the formation of lacquer deposits in engines. More specifically, this invention relates to a lubricating oil for natural gas engines that reduces cylinder liner lacquer deposits.
  • LHV is the HHV less the amount of heat used to evaporate the water formed by combustion and other entrained contaminants. More information and the calculation of LHV may be determined from ANSI/ASME B.133.7M-1985, which is herein incorporated by reference.
  • LHV The change in LHV has long been used to predict the combustion efficiency of natural gas engines.
  • An increase in LHV can lead to over temperature operation which may cause hot spots in the combustion chamber. If the gas engine is operated under this condition for a period of time, the useful life of its internal parts may be reduced.
  • the control system calls for an increase in fuel flow in order to maintain the power output of the engine, which may cause incomplete combustion and a drop in efficiency. In the case of very low LHV, the required fuel flow for maximum power output may exceed the specification of the fuel supply system and hence the desired power output may not be achieved.
  • the LHV is determined as above, and the p air and p ⁇ e ; are the density of the incoming air and fuel stream to the engine at standard conditions (101.3 kPa and 273.15 °K).
  • the standard metric units for the Wobbe Index (and the LHV) are MJoules/m . Further determination of the Wobbe Index may be found in SAE Technical Paper 861578, "Interchangeability of Gaseous Fuels - The Importance of the Wobbe-Index", 1986, which is herein incorporated by reference.
  • Lacquer is a deposit resulting from the oxidation and polymerization of fuels and lubricants when exposed to high temperatures. Noting that the term is often used interchangeably with varnish, the CRC Deposit Rating Manual 20 defines lacquer as "a thin, hard, lustrous, oil-insoluble deposit, composed primarily of organic residue, and most readily definable by color intensity. It is not easily removed by wiping with a clean, dry, soft, lint- free wiping material and is resistant to saturated solvents.
  • lacquer is known to form both on pistons and on the cylinder liners. While piston lacquer has often been discussed in the art, it differs from cylinder liner lacquer. Piston lacquer appears to be a high temperature phenomena, forming on the lands, grooves, skirt and undercrown of the piston. One current theory is that the formation of lacquer on these hot locations is a function of the oxidative stability of the lube oil. Therefore, a lubricating oil employing a Group II base oil should produce less piston lacquer than one employing a Group I base oil.
  • Cylinder liner lacquer is generally formed over the range of the top piston ring travel, that is, on the cylinder walls below the liner dead space (also known as the "squish area") and above the top compression ring at the bottom of piston travel.
  • liner dead space also known as the "squish area”
  • a partially clogged injector may lead to improper spray patterns. It is well known that irregular fuel impingement on the cylinder liner walls accelerates liner lacquer formation.
  • the lacquer will fill in the cylinder liner cross hatching grooves which are vital for providing a uniform, protective oil film.
  • Lube oil consumption a major operating cost for these engines, can increase dramatically. This may result in bore polish, scuffing and scoring of the cylinder liners. Contrary to the theory of lacquer formation on hot surfaces, it is theorized that the solubility characteristics of the base oil mixture are more important than its oxidative stability for cylinder liner lacquer formation.
  • a lubricating oil composition that performs adequately in one engine at given operating conditions does not necessarily perform adequately when used in a different engine or under different conditions. This is especially true for natural gas fueled engines. While theoretically, lubricants could be designed for each possible combination of engine and service condition, such a strategy would be impractical because many different types of engines exist and the engines are used under widely varying conditions. Accordingly, lubricants that perform well in different types of engines and across a broad spectrum of conditions (e.g., fuel type, operating load and temperature) are desired. Design of lubricating oil compositions is further complicated in that the concentrated mixture of chemicals added to lubricating oil base stocks to impart desirable properties should perform well over a broad range of different quality base stocks.
  • the present invention provides a method of reducing lacquer formation in an internal combustion engine by using a lubricant comprising: (a) at least about 20 wt% of at least one base oil of lubricating viscosity selected from the group consisting of Group II, Group III and Group IV base stocks;
  • the present invention more specifically provides a method of reducing cylinder liner lacquer in internal combustion engines employing the above formulation.
  • the present invention relates to a lubricating oil composition characterized in that the composition comprises a mixture of the following components:
  • the present invention relates to a lubricating oil composition characterized in that the composition comprises a mixture of the following components:
  • the present invention comprises a lubricating oil composition that reduces lacquering in natural gas powered engines characterized in that the composition comprises a lubricating base oil and a mixture of the following components: (a) at least about 40 wt% of at least one base oil of lubricating viscosity selected from the group consisting of Group II, Group III and Group IV base stocks;
  • One aspect of the present invention is an additive system for use in a lubricating oil comprising at least about 20% of a Group II base stock, said additive comprising portions (b) through (e) of the above formulations, alone or when in a diluent.
  • the present invention provides a method of reducing cylinder liner lacquer using the formulations outlined above.
  • the base oil for the lubricant of the present invention may be a mineral or synthetic oil or blends thereof, so long as about at least 20% is a non- Group I base stock as defined by API.
  • a wide range of base stocks and base oils are known in the art.
  • Base stocks and base oils that may be used as co-base stocks or co-base oils in combination with the base stocks and base oils of the present invention are natural oils, mineral oils, and synthetic oils. These lubricant base stocks and base oils may be used individually or in any combination of mixtures with the instant invention. Natural, mineral, and synthetic oils (or mixtures thereof) may be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil).
  • Unrefined oils are those obtained directly from a natural, mineral, or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property.
  • One skilled in the art is familiar with many purification processes. These processes include for example solvent extraction, distillation, secondary distillation, acid extraction, base extraction, filtration, percolation, dewaxing, hydroisomerization, hydro- cracking, hydrofinishing, and others.
  • Rerefined oils are obtained by processes analogous to refined oils but using an oil that has been previously used.
  • Groups I, II, III, IV and V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base stocks and base oils.
  • Group I base stocks generally have a viscosity index of between about 80 to 120 and contains greater than about 0.03 wt% sulfur and/or less than about 90% saturates.
  • Group II base stocks generally have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03 wt% sulfur and greater than or equal to about 90% saturates.
  • Group III stocks generally have a viscosity index greater than about 120 and contain less than about 0.03 wt% sulfur and greater than or equal to about 90% saturates.
  • Group IV includes polyalphaolefins (PAO).
  • Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five Groups. Table 1: API Classification of Base stocks and base oils
  • Base stocks and base oils may be derived from many sources. Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. In regard to animal and vegetable oils, those possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present invention. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
  • Synthetic oils include hydrocarbon oil.
  • Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, poly- propylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, polymers or copolymer of hydrocarbyl- substituted olefins where hydrocarbyl optionally contains O, N, or S, for example).
  • Polyalphaolefin (PAO) oil base stocks are a commonly used synthetic hydrocarbon oil.
  • PAOs derived from C8, CIO, C12, C14 olefins or mixtures thereof may be utilized. See U.S. Patents 4,956,122; 4,827,064; and 4,827,073, which are incorporated herein by reference in their entirety.
  • the PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifmoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifmoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trif
  • Other synthetic base stocks and base oils include hydrocarbon oils that are derived from the oligomerization or polymerization of low-molecular weight compounds whose reactive group is not olefinic, into higher molecular weight compounds, which may be optionally reacted further or chemically modified in additional processes (e.g. isodewaxing, alkylation, esterification, hydro- isomerization, dewaxing, etc.) to give a base oil of lubricating viscosity.
  • hydrocarbon oils that are derived from the oligomerization or polymerization of low-molecular weight compounds whose reactive group is not olefinic, into higher molecular weight compounds, which may be optionally reacted further or chemically modified in additional processes (e.g. isodewaxing, alkylation, esterification, hydro- isomerization, dewaxing, etc.) to give a base oil of lubricating viscosity.
  • Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g., waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof.
  • hydroisomerized waxy stocks e.g., waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • hydroisomerized Fischer-Tropsch waxes e.g., waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • Fischer-Tropsch waxes the high boiling point residues of Fischer- Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content.
  • the hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • an amorphous hydrocracking/hydroisomerization catalyst such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • LHDC specialized lube hydrocracking
  • a zeolitic catalyst preferably ZSM-48 as described in U.S. Patent 5,075,269.
  • Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes are described, for example, in U.S. Patents Nos. 2,817,693; 4,975,177; 4,921,594 and 4,
  • Gas-to-Liquids (GTL) base stocks and base oils may have useful pour points of about -20°C or lower, and under some conditions may have advantageous pour points of about -25°C or lower, with useful pour points of about -30°C to about -40°C or lower.
  • Useful compositions of Gas-to-Liquids (GTL) base stocks and base oils, Fischer-Tropsch wax derived base stocks and base oils, and wax isomerate hydroisomerized base stocks and base oils are recited in U.S. Patent Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and are incorporated herein in their entirety by reference.
  • diarylamines useful in this invention are well known antioxidants and there is no particular restriction on the type of diarylamine that can be used.
  • the diarylamine is a secondary diarylamine and has the general formula:
  • Rl and R2 each independently represents a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms.
  • substituents for the aryl group include aliphatic hydrocarbon groups such as alkyl having from about 1 to 30 carbon atoms, hydroxy groups, halogen radicals, carboxyl groups or nitro groups.
  • the aryl is preferably substituted or unsubstituted phenyl or naphthyl, particularly wherein one or both of the aryl groups are substituted with at least one alkyl having from 4 to 30 carbon atoms, preferably from 4 to 18 carbon atoms. It is further preferred that both aryl groups be substituted, e.g., alkyl substituted phenyl.
  • the diarylamines used in this invention can be of a structure other than that shown in the above formula that shows but one nitrogen atom in the molecule.
  • the diarylamine can be of a different structure provided that at least one nitrogen has 2 aryl groups attached thereto, e.g., as in the case of various diamines having a secondary nitrogen atom as well as two aryls on one of the nitrogens.
  • diarylamines used in this invention should be soluble in the formulated crankcase oil package.
  • examples of some diarylamines that may be used in this invention include: diphenylamine; various alkylated diphenylamines, 3-hydroxydiphenylamine; N-phenyl- 1 ,2-phenylenediamine; N-phenyl- 1 ,4- phenylenediamine; dibutyldiphenylamine; dioctyldiphenylamine; dinonyldi- phenylamine; phenyl-alpha-naphthylamine; phenyl-beta-naphthylamine; diheptyldiphenylamine; and p-oriented styrenated diphenylamine, mixed butyloctyldiphenylamine, and mixed octylstyryldiphenylamine.
  • Examples of commercial diarylamines include, for example, Irganox® L06 and Irganox® L57 from Ciba Specialty Chemicals; Naugalube® AMS, Naugalube® 438, Naugalube® 438R, Naugalube® 438L, Naugalube® 500, Naugalube® 640, Naugalube® 680, and Naugard® PANA from Uniroyal Chemical Company; Vanlube® DND, Vanlube® NA, Vanlube® PNA, Vanlube® SL, Vanlube® SLHP, Vanlube® SS, Vanlube® 81, Vanlube® 848, and Vanlube® 849 20 from R.T. Vanderbilt Company, Inc.
  • the concentration of the diarylamine in the lubricating composition can vary depending upon the customer's requirements and applications.
  • a practical diarylamine use range in the lubricating composition is from about 500 parts per million to 20,000 parts per million (i.e., 0.05 to 2.0 wt%) based on the total weight of the lubricating oil composition, preferably the concentration is from 1,000 to 10,000 parts per million (ppm) and more preferably from about 2,000 to 7,500 ppm by weight.
  • phenate means the broad class of metal phenates including salts of alkylphenols, alkylphenol sulfides, and the alkylphenol-aldehyde condensation products. Detergents formed from the polar phenate substrate may be overbased. Normal phenate has the structural formula:
  • R 3 and R 4 are individually alkyl groups preferably of eight or more carbon atoms
  • M is a metallic element (e.g., Ca, Ba, Mg)
  • x may range from 1 to 3 depending on the particular metal involved.
  • the calcium phenates is preferred for use in the present invention.
  • Overbased alkaline-earth metal phenates are often referred to by the amount of total basicity contained in the product. It is common to label a detergent by its TBN (total base number), i.e., a 300 TBN synthetic sulfonate. Base number is defined in terms of the equivalent amount of potassium hydroxide contained in the material. A 300 TBN calcium sulfonate contains base equivalent to 300 milligrams of potassium hydroxide per gram or, more simply, 300 mg KOH/g.
  • the alkaline-earth metal phenates useful in the present invention should have TBN's of from about 100 to 400, with 100 to 300 being more preferred. TBN's may be determined using ASTM D 2896.
  • the concentration of the alkaline-earth metal phenates in the lubricating composition can vary depending upon the customer's requirements and applications. In a preferred embodiment of the invention, a practical alkaline-earth metal phenates use range in the lubricating composition is from about 500 parts per million to 50,000 parts per million (i.e. 0.05 to 5.0 wt%) based on the total weight of the lubricating oil composition, preferably the concentration is from 7,500 to 40,000 parts per million (ppm) and more preferably from about 9,000 to 27,000 ppm by weight.
  • alkaline-earth metal phenates useful in the present invention fall into the general class of additives known as detergents, the phenates are not interchangeable with other detergents, i.e., sulfonates, as two detergents having the same TBN, molecular weight, metal ratio and the like, will have widely different performance characteristics in the present invention.
  • the metal sulfonate useful in the present invention is represented, e.g., by one of the general formulae
  • R 5 and R 6 are each a hydrocarbon group, which may be the same or different; and (n) is number of alkyl substituent(s) on the aromatic or naphthalene ring, and an integer of 1 to 5 or 1 to 7, respectively, preferably 1 to 2.
  • the hydrocarbon group is an alkyl or alkenyl group having a carbon number of 8 to 28, preferably an alkyl group having a carbon number of 10 to 22. When the carbon number is below 8, the metallic detergent may not be sufficiently dissolved in the lubricant oil.
  • the metal sulfonate of the present invention is preferably a calcium sulfonate made from the salt of sulfonic acid having a hydrocarbon group (e.g., petroleum-derived sulfonic acid, and sulfonic acid having a long-chain alkyl benzene and alkyl naphthalene), and is not overbased.
  • sulfonic acid having a hydrocarbon group e.g., petroleum-derived sulfonic acid, and sulfonic acid having a long-chain alkyl benzene and alkyl naphthalene
  • the metal sulfonate for the lubricant oil composition of the present invention is preferably a calcium sulfonate provided at 0.5 to 5.0 wt% as the total content based on the whole composition, preferably at 0.5 to 3.0 wt% as the total content based on the whole composition, and more preferably at 0.5 to 1.0 wt% as the total content based on the whole composition.
  • the detergent may have an insufficient lacquer control.
  • it exceeds 5.0 wt% on the other hand, its acid-neutralizing function may not increase as expected for its content, and may conversely cause problems, such as oxidation of the metallic detergent, deteriorating itself into a deposit.
  • Basic nitrogen-containing ashless dispersants useful in this invention include hydrocarbyl succinimides; hydrocarbyl succinamides; mixed ester/amides of hydrocarbyl-substituted succinic acids formed by reacting a hydrocarbyl-substituted succinic acylating agent stepwise or with a mixture of alcohols and amines, and/or with amino alcohols; Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines; and amine dispersants formed by reacting high molecular weight aliphatic or alicyclic halides with amines, such as polyalkylene polyamines. Mixtures of such dispersants can also be used.
  • aminoated hydrocarbyl succinic derivatives and “aminated polyalkenyl succinic derivatives” include all items listed in this paragraph.
  • Such basic nitrogen-containing ashless dispersants are well known lubricating oil additives, and methods for their preparation are extensively described in the patent literature.
  • hydrocarbyl-substituted succinimides and succinamides and methods for their preparation are described, for example, in U.S. Pat. Nos. 3,018,247; 3,018,250; 3,018,291; 3,172,892; 3,185,704; 3,219,666; 3,272,746; 3,361,673; and 4,234,435.
  • Mixed ester-amides of hydrocarbyl-substituted succinic acid are described, for example, in U.S. Pat. Nos. 3,576,743; 4,234,435 and 4,873,009.
  • Mannich dispersants which are condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines are described, for example, in U.S. Pat. Nos. 3,368,972; 3,413,347; 3,539,633; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 3,798,247; 3,803,039; 3,985,802; 4,231,759 and 4,142,980.
  • Amine dispersants and methods for their production from high molecular weight aliphatic or alicyclic halides and amines are described, for example, in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; and 3,565,804.
  • amines containing basic nitrogen or basic nitrogen and additionally one or more hydroxyl groups can be used in the formation of the ashless dispersants.
  • the amines are polyamines such as polyalkylene polyamines, hydroxy-substituted polyamines and polyoxyalkylene polyamines.
  • polyalkylene polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and dipropylene triamine.
  • Hydroxy-substituted amines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylene diamine, N-(2-hydroxyethyl) piperazine, and N-hydroxyalkylated alkylene diamines of the type described in U.S. Pat. No. 4,873,009.
  • Polyoxyalkylene polyamines typically include polyoxyethylene and polyoxypropylene diamines and triamines having average molecular weights in the range of 200 to 2500.
  • Borated polyalkenyl succinimides are described in U.S. Pat. No. 4,863,624, which is herein incorporated by reference.
  • Preferred borated dispersants are boron derivatives derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, polyoxy- ethylene amines, and polyol amines (PIBSA/PAM) and are preferably added in an amount from about 1.0 to 10.0 wt%, more preferably about 1.5-6.0 wt%, and even more preferably in the amount of 1.75-3.0 wt% based on oil composition. These reaction products are amides, imides or mixtures thereof. Borated dispersants may provide benefits over non borated equivalents with respect to corrosion, rust, seal swell and wear.
  • additives such as other antioxidants, pour point depressants, viscosity index improvers, metal passivators, defoamants, friction modifiers, thickeners, emulsifiers, demulsifiers, dyes, corrosion inhibitors, acid sequestration agents, extreme pressure agents may be added without affecting the lacquer reducing performance of the current invention.
  • Lacquer formation is generally not a problem in natural gas engines running clean, dry methane of high Wobbe Index numbers.
  • the present formulation would still be useful as it would reduce lacquer formation caused by the unusual circumstances of excessively high or low engine temperatures combined with a non-optimized air/fuel ratio.
  • the present invention is employed in natural gas engines that use less pure forms of natural gas, such as bio, wellhead, sewer, landfill and digester gas and other gas engines where lacquer formation is more often found.
  • the present invention is more useful when employing natural gas with a Wobbe Index of less than 30 MJoules/m 3 EXAMPLES
  • a Caterpillar G3616 gas powered engine was operated on landfill gas employing a commercially available lubricant that contained both Group I and Group II base oils and a conventional additive set. After 16,249 hours of operation, two of the power cylinders were overhauled. During this time, the lubricant consumption had risen from the typical seven gallons per day to approximately 10 gallons per day. The cylinder liners were removed and split. Sections from the ring travel area (expected area of heavy lacquer formation) and areas at the bottom of the liners (essentially no lacquer formation) were removed and measured for surface roughness.

Abstract

L'invention concerne des compositions d'huile lubrifiante qui s'avèrent réduire de manière surprenante la formation de dépôts de vernis dans les moteurs. L'invention concerne plus particulièrement une huile lubrifiante pour moteurs au gaz naturel, cette huile permettant de réduire les dépôts de vernis liés aux siloxanes dans les chemises de cylindre.
PCT/US2004/010221 2003-04-18 2004-04-02 Composition d'huile lubrifiante reduisant les depots de vernis et methode d'utilisation de cette composition WO2004094576A2 (fr)

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EP04759791A EP1615986A2 (fr) 2003-04-18 2004-04-02 Composition d'huile lubrifiante reduisant les depots de vernis et methode d'utilisation de cette composition
CA002519539A CA2519539A1 (fr) 2003-04-18 2004-04-02 Composition d'huile lubrifiante reduisant les depots de vernis et methode d'utilisation de cette composition

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US10/418,359 2003-04-18
US10/418,359 US20040209783A1 (en) 2003-04-18 2003-04-18 Lacquer reducing lubricating oil composition and method of use of same

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WO2004094576A3 WO2004094576A3 (fr) 2004-11-25

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US9567554B2 (en) * 2014-01-10 2017-02-14 General Electric Company Apparatus, method, and solvent for cleaning turbine components
US10336959B2 (en) 2015-07-16 2019-07-02 Afton Chemical Corporation Lubricants with calcium-containing detergent and their use for improving low speed pre-ignition
US10550349B2 (en) 2015-07-16 2020-02-04 Afton Chemical Corporation Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition
US10421922B2 (en) 2015-07-16 2019-09-24 Afton Chemical Corporation Lubricants with magnesium and their use for improving low speed pre-ignition
US10377963B2 (en) 2016-02-25 2019-08-13 Afton Chemical Corporation Lubricants for use in boosted engines
US11155764B2 (en) 2016-05-05 2021-10-26 Afton Chemical Corporation Lubricants for use in boosted engines
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US10443011B2 (en) * 2017-01-18 2019-10-15 Afton Chemical Corporation Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition
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EP1615986A2 (fr) 2006-01-18
US20040209783A1 (en) 2004-10-21
US20060084582A1 (en) 2006-04-20
CA2519539A1 (fr) 2004-11-04

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