DE102009019952A1 - Controlled release of additives in lubricant compositions for gas turbines - Google Patents

Abstract

A gas turbine lubricant composition includes a first lubricant composition and a delivery system for delivering at least one additive to said first lubricant composition in a controlled, delayed manner, thereby converting said first lubricant composition to a second lubricant composition different from said first lubricant composition. In one embodiment, the delivery system comprises a controlled release gel. A method of lubricating a gas turbine using this lubricant composition is also disclosed.

Description

The Disclosure relates to lubricant compositions for Gas turbines and in particular a delivery system for providing or refilling one or more desired ones Additives in such lubricant compositions.

A Gas turbine is a device that has an inflow of hot Combustion gases used in a stream of compressed air, Energy in the form of thrust, wave power and compressed Air, in any combination. The in the gas turbine flowing air is compressed in an air compressor and, usually at very high speeds, one Fed to the combustion chamber, where they mixed with fuel and ignited. The gases from the combustion chamber Turbine blades are fed and drive the turbine shaft at.

The Main function of the lubricant composition in the gas turbine is the cooling and lubricating of metal surfaces. A lubricant composition for a gas turbine with Good quality will essentially metal-to-metal contact prevent and enable the turbine with high efficiency over to operate for extended periods of time. Because gas turbines always become smaller and more efficient, the demands on the Lubricant composition increasingly demanding. stability and efficiency at higher shear forces, higher Press, and higher temperatures are just a few of the requirements for a lubricant composition for a gas turbine.

additionally The gas turbines are often operated in an extreme environment and changes in atmospheric pressure, changes temperature, water, seawater, dust, and a host of others Exposed to liquids and solid contaminants. consequently There is an increased need for lubricants for gas turbines that have improved oxidative and thermal Stability, corrosion resistance, resistance against silting and varnish, ability to fast Separation of water and bubbles inclusions, resistance against foaming and good anti-wear behavior. These demanding requirements continue to pose a challenge For example, it has been reported in the literature that a large Percentage of oil systems in gas turbines signs of decomposition, Loss of oxidative stability and formation of sludge and / or paint, even at an operating time of less than two years.

There The design of gas turbines is becoming increasingly complex It may be beneficial to the properties of the lubricant composition to tailor to specific components of the turbine. Each of these Components may require that the lubricant composition fulfills different functions and therefore an additive composition which differs from lubricant compositions, which is used in other parts of the turbine. It would be therefore advantageous, the composition of the lubricant within of the system.

The Revelation provides a dispensing system that is able to incorporate additives in lubricating oils or refill, and a method of using such Systems in a gas turbine.

In an exemplary embodiment, the method comprises for the lubrication of metal-to-metal interfaces in a gas turbine: (a) contacting a first lubricant composition with a delivery system, wherein the delivery system has at least one desired one Additive includes; (b) releasing the desired additives by the delivery system into the first lubricant composition, which This causes the first lubricant composition is converted into a second lubricant composition, wherein the second lubricant composition of the first lubricant composition different; and (c) circulating the second lubricant composition inside a gas turbine, the metal-to-metal interfaces having.

In In another embodiment, the dispensing system (s) comprises at least one additive selected from the group consisting from detergents, dispersants, acids, bases, overbased Detergents, succinylated polyolefins, viscosity modifiers, Friction modifiers, cloud point depressants ("cloud point depressants "), pour point-lowering (" pour point depressants "), demulsifiers, flow improvers, antistatic agents, antioxidants, antifoam agents, corrosion inhibitors, Antirust agents, extreme pressure agents, anti-wear agents, Seal swelling agents, lubricants, anti-fogging agents and Mixtures thereof.

In In another embodiment, the delivery system comprises an adjuvanted controlled release gel.

Either the preceding general description as well as the following Detailed descriptions are only as exemplary and explanatory to understand and aim to further explain the present disclosure as claimed.

The delivery system comprises at least one of the following: liquids, solids, a controlled-release additive gel, capsules (e.g., melamine or urea-formaldehyde microencapsulating polymers), polymer pouches (e.g., linear low density polyethylene), perforated Leaves, paddles, injectors, polymers which are oil permeable at elevated temperatures (as in U.S.P. U.S. Patent 4,066,559 defined), particles that are oil-insoluble, but oil-wettable (as in the U.S. Patent 5,478,463 oil-soluble solid polymers capable of serving as viscosity improvers (as defined in U.S.P. U.S. Patent 4,014,794 defined), or mixtures thereof. In one embodiment, the additive delivery system in the lubricant composition dissolves by contacting the additive delivery system with the lubricant composition. The additives may be delivered to the lubricant composition by any process or process, such as e.g. B. by dissolution in the lubricant composition.

in the Generally, additives in lubricant compositions toned down for gas turbines over time or used up. In an exemplary embodiment For example, the additive delivery system is specifically formulated to provide the desired Performance requirements of the gas turbine application, or even the specific components of a gas turbine. In a preferred embodiment, the additive delivery system becomes used to improve the performance of a lubricant composition for a gas turbine by refilling the used up desired additives / additives or by insertion a newly desired additive / additives in the composition to increase. Thus, the lubricant composition for add the gas turbine features and / or existing ones and / or the useful life of the composition, as well as the Service life and reliability of the turbine, this Uses composition, lengthen.

The Additive dispensing system is located at any point where the delivery system is in direct or indirect contact with the Lubricant composition will be. If, for example, oil-soluble solid polymers can be used as the delivery system these are discharged from the inside of an oil filter. In In another embodiment, it may be desirable be the delivery system in contact with the lubricant composition, for example, in a reservoir, or in a liquid Secondary circuit, to place. One or more positions in one Line, circuit and / or the lubricant system can Additive delivery system included. If still more than one additive delivery system for the lubricant composition for gas turbines used, the additive delivery systems may be identical, similar and / or be different additive delivery system compositions. It is advantageous to place the dispensing system in a place where it is easily accessible and replaced or refilled can be, if necessary.

In an embodiment include those of the desired Additive properties one or more of the following: Dispersibility, antioxidant, corrosion inhibition, prevention wear, prevention of abrasion, prevention from pitting, including micro- and macro-pitting, friction-changing Properties, including elevated and / or reduced coefficient of friction, cleaning power, viscosity control using viscosity modifiers, foam control or mixtures thereof.

In In one embodiment, the first lubricant composition in the second lubricant composition, different from the first Lubricant composition is different, converted. The transformation the first lubricant composition in the second lubricant composition can by releasing the desired additives from the Dispensing system in an amount that is sufficient to another Ratio of additives to be achieved. The change of the ratio of the additives by adding the desired additives can in one embodiment by adding or bringing the first lubricant composition into contact with a delivery system composition of the desired Additives and release of these additives into the first lubricant composition be achieved. In this way can be different Lubricating compositions containing different additives are delivered to specific components of the gas turbine, and tailor-made to the special requirements of these special components become.

In another embodiment, the line contains the circuit and / or the lubricant composition system two or more different additive delivery systems attached to two or more places are placed. The different compositions the additive delivery systems provide the first lubricant composition with the desired additives released in a controlled manner to convert them into a second lubricant composition. In one embodiment, a first lubricant composition is with a variety of delivery systems in contact, creating a conversion the first lubricant composition into a plurality of second Lubricant compositions results. In another embodiment is a variety of first lubricant compositions in Contact with a variety of delivery systems, creating a conversion of the first compositions in a variety of second compositions results. Furthermore, if a variety of delivery systems are used, Each can be configured to have one or more additives and the other delivery systems can be used to deliver the same or other additive (s).

In In one embodiment, the delivery system (s) may / may be positioned in a container. For example, it may be in an embodiment be desirable, a Container receiving the additive dispensing system, such as a housing, a canister or a net-like structure, at a position where it interacts with the lubricant composition for the gas turbine will be in contact, for example a canister within a secondary circuit. The necessary design feature for the container, that is at least part of the additive delivery system in contact with the lubricant composition for the Gas turbine is.

In In one embodiment, the dispensing system controls releasing gel. The gel comprises at least two components, which, when combined, form a gel. The gel-forming components can be selected from the group consisting from detergents, dispersants, acids, bases overbased Detergents, succinylated polyolefins or mixtures thereof. The gel optionally, but preferably, contains at least one Additive selected from the group consisting of viscosity modifiers, Friction modifiers, detergents, cloud point depressants, Pour point depressants, demulsifiers, flow improvers, antistatic agents, dispersants, antioxidants, antifoams, Corrosion / rust inhibitors, high pressure / antiwear agents, Seal swelling agents, lubricants, anti-fogging agents, or mixtures thereof.

The controlled release gel must be in contact with the lubricant composition stand. In one embodiment, the controlled release Gel in direct contact with the lubricant composition in a range of approximately 100% to approximately 1% the lubricant composition in the system, and all areas between. In another embodiment, this is controlled releasing gel in direct or indirect contact with the lubricant composition in a range of about 75% to about 25% of the lubricant composition in the system and in one Another embodiment is the controlled release Gel in contact with the lubricant composition in a range of about 50% of the lubricant composition in the System. The controlled release gel can by any known Method to be added to the system depends from the total amount of gel released over time should be the desired form of the controlled releasing gel (eg stiffness, consistency, homogeneity and the like), the desired total solubility of the gel, the desired release rate of a specific Component, the desired type of operation and / or each Combination of the above.

The Release rate of the controlled release gel is primarily due to the controlled release gel formulation certainly. The release rate also depends on the way of adding the controlled release gel, the placement the controlled release gel, the flow rate the lubricant composition, the form of the controlled release Gels and the like off. The controlled release gel is in a suitable location for the specific and desired Dissolution rate of controlled release Placed gel components.

The formulation of the controlled release gel may include components that dissolve at different release rates in the lubricant composition. Thus, the gel would contain components that dissolve rapidly in the lubricant composition, or not at all. Those that do not dissolve would remain for the useful life of the lubricant composition, whereas others would be consumed over time. The gel may be formulated to provide the desired dissolution characteristics under specific conditions, such as the flow rate over the surface of the gel, or, for example, the temperature. For example, in one embodiment, the gel may be formulated so that all the components of the gel slowly into of the heated lubricant composition to allow slow and selective release of the desired additives into the lubricant composition. The rate of release can be optimized so that the desired gel component (s) are released over a substantial portion up to the total useful life of the lubricant composition.

The Gel can be used as it is without an inert carrier or a non-additive matrix, such as a polymeric one Membrane or complicated mechanical systems that are in the state of Technique to achieve a controlled release of the additives over a period are necessary.

In one embodiment, the gel is a mixture of two or more gel-forming components and optionally at least one functional additive from the above-mentioned group. The gel exists in a semi-solid state more like a solid than a liquid, see Parker, Dictionary of Scientific and Technical Terms, 5th Edition, McGraw Hill (1994) ; see also Larson, "The Structure and Rheology of Complex Fluids", ch. 5, Oxford University Press, New York, NY (1999) , all of which are hereby incorporated by reference. The rheological properties of a gel can be measured in periodic shear fields with small amplitude. This technique measures the structural property of the gel and provides a quantity called the storage modulus, which represents the reservoir of elastic energy, and the loss modulus, which represents the viscous dissipation of that energy. The ratio of the loss modulus / storage modulus, called loss factor or "tan delta", is> 1 for materials that are liquid-like and <1 for materials that are similar to solids. The controlled release gels in one embodiment have tan delta values of about ≤0.75, in another embodiment about ≤-0.5, and in another embodiment about ≤0.3.

In In one embodiment, the additive gel comprises: (i) at least two additives selected from the group consisting of Detergents, dispersants, acids, bases, overbased Detergents, succinylated polyolefins, or mixtures thereof, wherein the selected additives form a gel when they to be united; and (ii) optionally at least one additive from the group consisting of viscosity modifiers, Friction modifiers, detergents, cloud point depressants, Pour point depressants, demulsifiers, flow improvers, antistatic agents, dispersants, antioxidants, antifoams, Corrosion / rust inhibitors, high pressure / antiwear agents, Seal swelling agents, lubricants, anti-fogging agents or mixtures thereof. In one embodiment the components of group (i) about 0.01% to about 95% of the total weight of the gel. In another embodiment For example, the components of group (i) comprise about 0.1% to 80% of the total weight of the gel and in another embodiment from 1% to about 50% of the total weight of the Gel.

If present, the optional components of group (ii) in suitable percentages necessary to the Lubricant composition to supply the desired amount of additives, for example, from about 0.1% to about 95%, or about 0.1% to 90%, or about 0.1% to about 80%, or about 0.5% to about 50% of the total weight of the gel.

The Additive gel may be at least two in one embodiment Additives comprise, selected from the group, the detergents, Dispersants, acids, bases, overbased Detergents, succinylated polyolefins or mixtures thereof, these selected additives form a gel when they are united. Every delivery system that comes from a combination is formed from two or more additives containing detergents, dispersants, Acids, bases, overbased detergents, succinylated Polyolefins and the like may be used for the preparation of the additive gel. Furthermore, the additive gel includes in one embodiment, combining dispersants, or combining a dispersant and an acid, or combining a dispersant and a base, or a dispersant and an overbased detergent, and similar.

In In one embodiment, the category of gels finds particularity Application in which the gelation through a combination of overbased Detergent and ashless succinimide dispersant is effected. In one embodiment, the ratio of Detergent to dispersant of about 10: 1 to about 1:10, in another embodiment approximately 5: 1 to about 1: 5, from about 4: 1 to about 1: 1 and in another embodiment approximately 4: 1 to about 2: 1. In addition amounts the TBN of the overbased detergent attached to the gel formation matrix usually at least 200, more usual 300 to 1,000 and most typically 350 to 650. If mixtures of overbased Detergents should be used, at least one should have a TBN value within these ranges. However, even the average TBN of this mixture correspond to these values.

The Dispersant includes dispersant; dispersants in ashless form, such as Mannich dispersant; polymeric dispersants; carboxylic dispersants; Amine dispersant, ester high molecular weight (i.e., at least 12 carbon atoms) and similar; esterified maleic anhydride-styrene copolymers; maleated ethylene-diene monomer copolymers; surfactants; emulsifiers; functionalized Derivatives of each of the components listed here and the like; and combinations and mixtures thereof. The dispersant can be used alone or in combination. In one embodiment For example, the preferred dispersant is a polyisobutenyl succinimide dispersant. The polyisobutenyl substitution on the succinimide may also be of so-called highly reactive polyisobutenes, which are more than 70% have terminal vinylidene groups.

The Dispersant includes ashless dispersants, such as polyisobutenyl succinimide and the like, but is not limited to these. Ashless polyisobutenyl succinimide dispersant are commercially available products that are typically by reaction of polyisobutylene having an average molecular weight ("Mn") of about 300 to 10,000 with Maleic anhydride to polyisobutenyl succinic anhydride ("PIBSA") and subsequent implementation of the product thus obtained with a polyamine, which is typically Contains 1 to 10 ethyleneamino groups per molecule, to be obtained.

Ashless-type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Succinimide dispersants are in the U.S. Patent 4,234,435 , which is incorporated by reference, more fully described.

The Mannich dispersants are reaction products of alkylphenols, in which the alkyl group has at least about 30 carbon atoms comprising, with aldehydes (especially formaldehyde) and amines (in particular Polyalkylene polyamines).

Another class of dispersants are carboxylic dispersants. Examples of these "carboxylic dispersants" are in U.S. Patent 3,219,666 described.

Amine dispersants are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples of this are in the U.S. Patent 3,565,804 described.

Polymeric dispersants are interpolymers of oil-soluble monomers such as decyl methacrylate, vinyl decyl ethers and high molecular weight olefins with monomers containing polar substituents, e.g. As aminoalkyl acrylates or acrylamides and poly (oxyethylene) -substituted acrylates. Examples of these polymer dispersants are shown in the following U.S. Patents 3,329,658 and 3,702,300 disclosed.

dispersants can also by reaction with each of a variety be aftertreated by agents. Among these are urea, Thiourea, dimercaptothiazoles, carbon disulfide, aldehydes, Ketones, carboxylic acids, hydrocarbon-substituted Succinic anhydrides, nitriles, epoxides, boron compounds and phosphorus compounds.

dispersants can be used alone or in combination. The Dispersant is in a range of about zero Wt .-% or 0.01 wt .-% to about 95 wt .-% of the gel before, in another embodiment, in one area from about 1% to about 70% by weight of the Gels, and preferably in another embodiment in a range of about 5 wt% to about 50% by weight of the gel.

The detergents include overbased sulfonates, phenates, salicylates, carboxylates, overbased calcium sulfonate detergents, which are commercially available, overbased detergents containing metals such as Mg, Ba, Sr, Na, Ca and K, as well as mixtures thereof and the like. Detergents are for example in the U.S. Patent 5,484,542 described, the disclosure of which is incorporated herein by reference. The detergents can be used alone or in combination. The detergents are present in a range of about 0.05% to about 25% by weight of the gel, in one embodiment in a range of about 0.1% to about 15% by weight of the gel and in another embodiment, in a range of about 1.0% to about 5.0% by weight of the gel.

Typically, the controlled release gel will further contain at least one desired additive for the controlled release into the lubricant composition. Components desired for the additive gel include one or more viscosity modifiers, friction modifiers, detergents, cloud point depressants, pour point depressants, demulsifiers, flow improvers, antistatic agents, dispersants, antioxidants, antifoams, corrosion / rust inhibitors, high pressure / antiwear agents Seal swelling agents, lubricants, anti-fogging agents, and mixtures thereof; wherein a controlled release gel results, which releases the desired additive (s) into a lubricant composition over a period of time when the gel is contacted with the lubricant composition. The desired additive component is further determined by the lubricant composition formulation, performance characteristics, function, and the like, and which additive is to be added as an additive for spent additives and / or newly added additives, depending on the desired functions.

antioxidants include alkyl-substituted phenols, such as 2,6-di-tert-butyl-4-methylphenol, phenolate sulfides, phosphosulfurized Terpenes, sulfurized esters, aromatic amines, diphenylamines, alkylated Diphenylamines and hindered phenols, bis-nonylated diphenylamine, Nonyldiphenylamine, octyldiphenylamine, bis-octylated diphenylamine, bis-decylated diphenylamine, decyldiphenylamine and mixtures thereof one.

The Antioxidant function includes sterically hindered phenols and includes 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, 2,6-di-tert-butylphenol, 4-pentyl-2,6-di-tert-butylphenol, 4-hexyl-2,6-di-tert-butylphenol, 4-heptyl-2,6-di-tert-butylphenol, 4- (2-ethylhexyl) -2,6-di-tert-butylphenol, 4-octyl-2,6-di-tert-butylphenol, 4-nonyl-2,6-di-tert-butylphenol, 4-decyl-2,6-di-tert-butylphenol, 4-undecyl-2,6-di-tert-butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, 4-tridecyl-2,6-di-tert-butylphenol, 4-tetradecyl-2,6-di-tert-butylphenol including but not limited to, as well as sterically hindered Methylene-bridged phenols including 4,4-methylenebis (6-tert-butyl-o-cresol), 4,4-methylenebis (2-tert-amyl-o-cresol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), 4,4-methylene bis (2,6-di-tert-butylphenol), without being limited thereto to be, as well as mixtures thereof. Another example of an antioxidant is a hindered, ester-substituted phenol, which by Heating a 2,6-dialkylphenol with an acrylate ester under basic Conditions, such as aqueous KOH can be.

antioxidants can be used alone or in combination. The Antioxidants are typically in a range of about 0 wt .-% or up to about 30 wt .-% present, in one Embodiment in a range of approximately 0.05% to 25% by weight, and in another embodiment in a range of about 0.1 wt% to about 15 wt .-%, and in another embodiment in one Range from about 1.0% to about 5.0 Wt .-% total weight of additives.

The High pressure (extreme pressure, "EP") / anti-wear agent include sulfur or chlorosulfine EP agents, a chlorinated Hydrocarbon EP agents, or a phosphorylated EP agent or mixtures thereof. Examples of such EP agents are Amine salts of phosphoric acid, chlorinated waxes, organic Sulfides and polysulfides such as benzyl disulfide, bis (chlorobenzyl) disulfide, Dibutyl tetrasulfide, sulfurized walrat oil, sulfurized Methyl esters of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; Phosphosulfurierte hydrocarbons, such as the reaction product of phosphorus sulphide with turpentine or methyloleate, phosphorus esters, such as dicarboxylic and trihydrocarbyl phosphates, d. H. Dibutyl phosphate, diheptyl phosphate, dicyclohexyl phosphate, pentyl phenyl phosphate; Dipentylphenyl phosphate, tridecyl phosphate, distearyl phosphate and polypropylene-substituted phenol phosphates, metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenol diacid, such as zinc dicyclohexyl phosphorodithioates and zinc salts the phosphorodithioic acid combination and mixtures thereof can be used. A particularly useful EP agent is dimethyloctylphosphonate.

In One embodiment includes the antiwear / extreme pressure agent an amine salt of a phosphoric acid ester. The amine salt of Phosphoric acid ester includes phosphoric acid ester and salts thereof; Dialkyldithiophosphoric and Salts thereof; phosphites; and phosphorus-containing carboxyl esters, ethers and amides; and mixtures thereof.

In In one embodiment, the phosphorus compound further comprises a sulfur atom in the molecule. In one embodiment the amine salt of the phosphorus compound is ashless, d. H. metal-free (before mixing with other components).

The Amines suitable for use as amine salt include primary amines, secondary amines, tertiary Amines and mixtures thereof. The amines close those with at least one hydrocarbon group or, in certain Embodiments, two or three hydrocarbon groups one. The hydrocarbon groups can be approximately From 2 to about 30 carbon atoms, or in other embodiments about 8 to about 26, or about 10 to about 20, or about 13 to about Contain 19 carbon atoms.

Primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine and dodecylamine, as well as fatty amines such as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleylamine. Other useful fatty amines include commercially available fatty amines, such as ^Armeen® Amines (products available from Akzo Chemicals, Chicago, III.), Such as ^Armeen® C, ^Armeen® O, ^Armeen® OL, ^Armeen® T, ^Armeen® HT, ^Armeen® S and ^Armeen® SD, where the letter designation refers to the fatty group, such as coconut, oleyl, tallow or stearyl groups.

Examples suitable secondary amines include dimethylamine, Diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, Diheptylamine, methylethylamine, ethylbutylamine and ethylamylamine one. The secondary amines can be cyclic amines such as piperidine, piperazine and morpholine.

The Amines can also be tertiary aliphatic primary Be amines. The aliphatic group may in this case be an alkyl group that's about 2 to about 30, or about 6 to about 26, or about 8 to about Contains 24 carbon atoms. Tertiary alkylamines include monoamines such as tert-butylamine, tert-hexylamine, 1-methyl-1-aminocyclohexane, tert-octylamine, tert-decylamine, tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine and tert-octacosanylamine.

Mixtures of amines may also be used in the embodiments. In one embodiment a useful mixture of amines "Primene 81R ^®" and "Primene JMT 81R ^®" (both manufactured and sold by Rohm & Haas), which are mixtures of C ₁₁ - to C ₁₄ -tertiary Alkylprimäraminen or C ₁₈ - to C ₂₂ tertiary alkyl primary amines.

Suitable hydrocarbylamine salts of the alkylphosphoric acid according to the invention can be represented by the following formula (R ₄ O) (R ₃ O) PO _2. (R ₅ ) (R ₆ ) (R ₇ ) NH ⁺ wherein R ₃ and R _{4 are} independently Are hydrogen or hydrocarbon groups such as alkyl groups; for the phosphoric acid ester, at least one of R ₃ and R _{4 will be} a hydrocarbon radical. R ₃ and R ₄ may contain about 4 to about 30, or about 8 to about 25, or about 10 to about 20, or about 13 to about 19 carbon atoms. R ₅ , R ₆ and R ₇ may independently be hydrogen or hydrocarbon groups such as branched or linear alkyl chains of 1 to about 30, or about 4 to about 24, or about 6 to about 20, or about 10 to about 16 carbon atoms. These R ₅ , R ₆ and R ₇ groups may be branched or linear groups, and in specific embodiments at least one, or alternatively two of R ₅ , R ₆ or R _{7 is} hydrogen. Examples of alkyl groups which are suitable for R ₅ , R ₆ and R ₇ include butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl , 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexydecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl and eicosyl groups and mixtures thereof.

In one embodiment, the hydrocarbyl amine salt of an alkylphosphoric ester is the reaction product of a C ₁₄ - to C ₁₈ alkylated phosphoric acid with Primene 81R ^®.

Likewise, the hydrocarbon amine salts of the dialkyldithiophosphoric acid esters of the invention used in the anti-rust unit may be represented by the formula (R ₄ O) (R ₃ O) PS _2. (R ₅ ) (R ₆ ) (R ₇ ) NH ⁺ wherein the various R groups are as defined above, although typically both R groups are hydrocarbyl or alkyl groups. Examples of hydrocarbon amine salts of the dialkyl dithiophosphoric acid esters include the reaction product (s) of hexyl, heptyl or octyl, or nonyl, 4-methyl-2-pentyl or 2-ethylhexyl, isopropyl dithiophosphoric acids with ethylenediamine, morpholine or Primene 81 ^®, and mixtures thereof.

In one embodiment, the diphosphonic acid can be reacted with an epoxide or a glycol. The reaction product is further reacted with a phosphoric acid, an anhydride or a lower ester. The epoxide includes an aliphatic epoxide or a styrene epoxy. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecenyloxide, styrene oxide and the like one. In one embodiment, the epoxide is propylene oxide. The glycols may be aliphatic glycols of from 1 to about 12, or from about 2 to about 6, or about 2 to about 3 carbon atoms. The dithiophosphoric acids, glycols, epoxides, inorganic phosphorus reagents and methods for their implementation are described in US Pat U.S. Patents 3,197,405 and 3,544,465 described. The resulting acids can then be salted out with amines. An example of a suitable dithiophosphoric acid is prepared by adding phosphorus pentoxide (about 64 g) at about 58 ° C over a period of about 45 minutes to about 514 g of hydroxypropyl O, O-di (4-methyl-2-pentyl) phosphorodithioate by reaction of di (4-methyl-2-pentyl) phosphorodithioic acid with about 1.3 moles of propylene oxide at about 25 ° C). The mixture is heated at about 75 ° C for about 2.5 hours, mixed with silica and filtered at about 70 ° C. The filtrate contains about 11.8 weight percent phosphorus, about 15.2 weight percent sulfur, and an acid number of 87 (bromophenol blue).

The EP / antiwear agent can be used alone or in combination be used. In one embodiment, the EP / antiwear agent is present in a range of about 0.05 wt% to about 25 wt .-% before, in one embodiment in one area from about 0.1% to about 15% by weight and in another embodiment in a range of about 1.0% to about 5.0% by weight of the total weight of additives.

The Antifoam includes organic silicones, such as Polydimethylsiloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates and polymethacrylates, trimethyl-trifluoropropylmethylsiloxane and the like.

The Antifoam additives may be used alone or in combination become. The antifoam agent can be used in amounts that necessary to get the desired benefit and functionality to allow, and the specific concentrations for Each additive is within the skill of one of ordinary skill in the art.

Of the Viscosity modifier allows both viscosity-improving Properties as well as dispersing properties. Examples of closing dispersing viscosity modifiers Vinylpyridine, N-vinylpyrrolidone and N, N'-dimethylaminoethyl methacrylate and are examples of nitrogen-containing monomers and the same. Polyacrylates obtained by polymerization or copolymerization are obtained from one or more alkyl acrylates are also useful as a viscosity modifier.

Functionalized polymers can also be used as viscosity modifiers. Among the common classes of such polymers are olefin copolymers and acrylate or methacrylate copolymers. For example, functionalized olefin copolymers may be interpolymers of ethylene and propylene grafted with an active monomer such as maleic anhydride and then derivatized with an alcohol or an amine. Other such copolymers are copolymers of ethylene and propylene, which are reacted or grafted with nitrogen compounds. Derivatives of polyacrylate esters are well known as dispersing viscosity index modifier additives. Acrylic or polymethacrylate dispersant viscosity modifiers such as Acryloid ^™ 985 or Viscoplex ^™ 6-054 from RohMax are particularly useful. Solid oil-soluble polymers such as PIB (polyisobutylene), methacrylate, polyalkylstyrene, ethylene / propylene and ethylene / propylene / 1,4-hexadiene polymers, and maleic anhydride-styrene interpolymers and derivatives thereof can also be used as a viscosity index improver become. The viscosity modifiers are known and commercially available.

The Viscosity modifiers may be alone or in Combination can be used. The viscosity modifiers are in the range of about 0.05 wt% to about 25% by weight, and in one embodiment in one range from about 0.1% to about 15% by weight and in another embodiment in a range of from about 1.0% to about 5.0% by weight of the Total weight of additives before.

The Friction modifiers include organo-molybdenum compounds, including molybdenum dithiocarbamates, molybdenum carboxylates, Molybdenum amides, tungsten esters and fatty acid based Materials, including those based on linoleic acid, oleic acid, including glycerol monooleate (GMO), which is based on stearic acid based and the like.

In one embodiment, the friction modifier is a phosphate ester or salt, including a monohydrocarbyl, dihydrocarbyl or trihydrocarbyl phosphate wherein each hydrocarbyl group is saturated. In some embodiments, each of the hydrocarbyl groups contains from about 8 to about 30, or from about 12 to about 28, or from about 14 to about 24, or from about 14 to about 18 carbon atoms. In one embodiment, the hydrocarbyl groups are alkyl groups. Examples of the hydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl groups and mixtures thereof.

In one embodiment, the phosphate salts may be prepared by reacting an acidic phosphate ester with an amine compound or a metallic base to form an amine or a metal salt. The amines can be monoamines or polyamines. Useful amines include those amines that are used in the U.S. Patent 4,234,435 in Sp. 21, line 4, to Sp. 27, line 50. Useful amines include primary ether amines, such as those represented by the formula R "(OR ') _x --NH ₂ wherein R' represents a divalent alkylene group having from about 2 to about 6 carbon atoms; x is a number from 1 to about 150, or from about 1 to about 5, or 1; and R "is a hydrocarbon group of from about 5 to about 150 carbon atoms.

The Phosphate salt may be derived from a polyamine. The polyamines include alkoxylated diamines, fatty polyamine diamines, alkylene polyamines, Hydroxy-containing polyamines, condensed polyamines, aryl polyamines and heterocyclic polyamines.

The Metal salts of phosphoric acid esters are formed by reaction a metal base made with an acidic phosphorus ester. The Metal base can be any metal compound that is able to form a metal salt. Close examples of metal bases Metal oxides, hydroxides, carbonates, borates and the like. Suitable metals include alkali metals, alkaline earth metals and transition metals. In one embodiment For example, the metal is a Group IIA metal, such as calcium or magnesium, a Group IIB metal, such as zinc, or a group of VIIB metal, such as manganese. Examples of metal compounds that reacted with the phosphoric acid include zinc hydroxide, zinc oxide, copper hydroxide or copper oxide.

In In one embodiment, the friction modifier is a Phosphite and may be monohydrocarbyl, dihydrocarbyl or trihydrocarbyl phosphite wherein each hydrocarbyl group is saturated. In some Embodiments may be any hydrocarbyl group independently from about 8 to about 30, or about 12 up to about 28, or from about 14 to to about 24, or from about 14 to to about 18 carbon atoms. In one embodiment the hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl and octadecyl groups and mixtures thereof.

In one embodiment, the friction modifier is a fatty imidazoline containing fatty substituents of from 8 to about 30, or having from about 12 to about 24 carbon atoms. The substituent may be saturated or unsaturated, preferably saturated. In one aspect, the fatty imidazolines can be prepared by reacting a fatty carboxylic acid with a polyalkylene polyamine, such as those described above. Suitable fatty imidazolines include those in the U.S. Patent 6,482,777 one described.

The Friction modifiers can be used alone or in combination be used. The friction-reducing agents can used in quantities that are necessary to the desired Benefits and functionalities available too and specific concentrations for each additive are known in the art.

The antifog agents include very high molecular weight (> 100,000 Mn) polyolefins such as 1.5 Mn polyisobutylene (for example the material with the trade name Vistanex ^®), or polymers containing 2- (N-acrylamido), 2-methyl propane sulfonic acid (also known as AMPS) or derivatives thereof and the like.

The Anti-fogging agents may be used alone or in combination become. The anti-fogging agents can be used in quantities which are necessary to get the desired benefits and provide functionalities, and specific concentrations for each additive are known in the art.

The corrosion inhibitors include alkylated succinic acids and anhydride derivatives thereof, organophosphonates and the like. The rust inhibitors may be used alone or in combination. The rust inhibitors range from about 0.05% to about 25% by weight, and in one embodiment from about 0.1% to about 15% by weight, and in another embodiment in a range from about 1.0% to about 5.0% by weight of the total weight of additives.

The Metal deactivators include derivatives of benzotriazoles, such as tolyltriazole, N, N-bis (heptyl) -ar-methyl-1H-benzotriazole-1-methanamine, N, N-bis (nonyl) -ar-methyl-1H-benzotriazole-1-methanamine, N, N-bis (decyl) -ar-methyl-1H-benzotriazole-1-methanamine, N, N- (undecyl) -ar-methyl-1H-benzotriazole-1-methanamine, N, N-bis (dodecyl) -ar-methyl-1H-benzotriazole-1-methanamine, N, N-bis (2-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine and Mixtures thereof. In one embodiment, the Metal deactivator N, N-bis (1-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine; 1,2,4-triazoles, benzimidazoles, 2-alkyl-dithiobenzimidazoles; 2-alkyl-dithiobenzothiazole; 2-N, N-dialkyl-dithiocarbamoyl) benzothiazole; 2,5-bis (alkyl-dithio) -1,3,4-thiadiazoles, such as 2,5-bis (tert-octyl-dithio) -1,3,4-thiadiazole; 2,5-bis (tert-nonyl dithio) -1,3,4-thiadiazole; 2,5-bis (tert-decyl-dithio) -1,3,4-thiadiazole; 2,5-bis (tert-undecyl-dithio) -1,3,4-thiadiazole; 2,5-bis (tert-dodecyl-dithio) -1,3,4-thiadiazole; 2,5-bis (tert-tridecyl-dithio) -1,3,4-thiadiazole; 2,5-Bis (tert-tetradecyl-dithio) -1,3,4-thiadiazole; 2,5-bis (tert-octadecyl-dithio) -1,3,4-thiadiazole; 2,5-bis (tert-nonadecyl-dithio) -1,3,4-thiadiazole; 2,5-bis (tert-eicosyldithio) -1,3,4-thiadiazole and mixtures thereof, 2,5-bis (N, N-dialkyl-dithiocarbamoyl) -1,3,4-thiadiazole; 2-alkyldithio-5-mercapto-thiadiazoles and the same.

The Metal deactivators can be used alone or in combination be used. The metal deactivators can be used in quantities be used, which are necessary to the desired To provide benefits and functionalities, and specific ones Concentrations for each additive are known to those skilled in the art.

The Demulsifiers include polyethylene and polypropylene oxide copolymers and the like. The demulsifiers can be alone or be used in combination. Close the lubricant additives Glycerol monooleate, sorbitan monooleate and the like. The lubricant additives can be used alone or in combination. The Flow improvers include ethylene-vinyl acetate copolymers and the like. The flow improvers can used alone or in combination. The cloud point depressants include alkylphenols and their derivatives, ethylene-vinyl acetate copolymers and the like. The cloud point depressants can used alone or in combination. Close the pour point depressors Alkylphenols and their derivatives, ethylene-vinyl acetate copolymers and the like. The pour point depressors can be alone or used in combination. The seal swell agents include organosulfur compounds, such as thiophene, 3- (decyloxy) tetrahydro-1,1-dioxide, Phthalates and the like. The seal swelling agents can used alone or in combination. These additives can used in quantities that are necessary to the desired Benefits and functionalities available too and specific concentrations for each additive are known in the art.

optional may add other components to the delivery system These are basic stock oil, inert Carriers, dyes, bacteriostatic agents, solid particulate Additives and the like, as long as these components are not harmful Have an effect on the delivery system.

If the delivery system is a gel typically contains the gel small amounts (about 5 to 40% by weight) of basic stock oils, which mineral-based, synthetic (including synthetic Fischer-Tropsch gas-to-liquid process as well as other gas-to-liquid oils) or mixtures including but not limited to are.

Optionally, if desired, an inert support can be used. Furthermore, other active ingredients which provide a beneficial and desired function may also be included in the gel. In addition, solid particulate additives such as PTFE, MoS ₂ and graphite may also be included.

optional Dyes can be used and close Halo-alkanes and the like. The dyes can used alone or in combination. Optionally Bacteriostatic agents are used and close Formaldehyde, glutaraldehyde and their derivatives, and the like. The bacteriostatic agents may be used alone or in combination be used. These additives can be used in quantities which are necessary to get the desired benefits and to provide functionalities and specific concentrations for these additives well known to the skilled person.

The components are successively or all mixed together once to form a mixture. After mixing the components of the gel, a curing step may be required to effect gelation. If a curing step occurs, it will typically be in a range of approximately 20 ° C to about 165 ° C for about 1 minute to about 60 days, or at about 50 ° C to about 120 ° C for about 1 to about 24 hours, or about 85 ° C to about 115 ° C for about 4 to about 12 hours.

Examples

One Lubricant additive concentrate, which is used here in a Lubricant composition is suitable in a gas turbine enabled a reduced formation of sludge and varnish, without the oxidative stability to endanger, and includes a mixture of a phenolic Antioxidant (preferably 2,6-di-tert-butylphenol), tolyltriazole, dialkylaminomethylated tolytriazole and nonyl-diphenylamine.

One or more of these preferred materials can be found here be given off by a gel to be with others desired Components in the lubricant composition for gas turbines to be combined.

A gel is made with the following ingredients: ingredients Amount (wt%) Overbased detergent 45 20,000 MW (molecular weight) polyisobutenyl succinimide 10 Succinimide dispersant fifteen Anti-flame mixture (mixture of 2,6-di-tert-butylphenol, tolytriazole, dialkylaminomethylated tolytriazole and nonyldiphenylamine) 30

The gel is contacted with a gas turbine lubricant composition having the following composition: component amount (Wt .-%) Sample 1 Sample 2 Irgamet ^® 39 (corrosion inhibitor) 0.04 Aromatic 200 ND (diluent) 0.234 0.1 Emkarox ^® VG 380 (demulsifier) 0.01 0.01 HiTEC ^® 536 (rust inhibitor) 0.096 0.096 PANA (Amine Antioxidant) 0.083 0.0 Motiva Star 6 99.577 99.754

Exemplary compositions are tested for 1 week for varnish formation using the "Nippon Oil Color (NOC)" test. The examples are subjected to a "Rotarg Pressure Vessel Oxidation Test (RPVOT)" according to ASTM D2272 subjected. The results are shown in Table 1. The measurements in Table 1 show that the sustained-release gel can effectively release sludge and varnish reducing agents into the gas turbine lubricating composition. Table 1 NOC 150 C (1 week) Sample 1 Sample 2 initial color 0.5 0.3 End Color 7 5 Weight of Mud (mg) 4.36 1.96 Acid number (Tan D3339) 0.04 0.03 KV 40 44,01 44.25 Cop 2E 2E Δa (redness) 7.68 12.52 Δb (yellowish) 19.59 31.19 E (Euclidean distance between two colors) 53.09 49.32 RPVOT (Min) 1099 975

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 4066559 [0011]
• US 5478463 [0011]
• US 4014794 [0011]
• - US 4234435 [0030, 0062]
• US 3219666 [0032]
• - US 3565804 [0033]
• - US 3329658 [0034]
• US 3702300 [0034]
• - US 5484542 [0037]
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Cited non-patent literature

• Parker, Dictionary of Scientific and Technical Terms, 5th Edition, McGraw Hill (1994) [0023]
• Larson, "The Structure and Rheology of Complex Fluids", ch. 5, Oxford University Press, New York, NY (1999). [0023]
• ASTM D2272 [0083]

Claims (15)

Lubricant composition for gas turbines, comprising a first lubricant composition and a delivery system for dispensing at least one additive to this first lubricant composition in a controlled, delayed manner, causing these first lubricant composition in a second lubricant composition is converted, which is this second lubricant composition different from the first lubricant composition. A lubricant composition for gas turbines according to claim 1, wherein the delivery system comprises a gel. A lubricant composition for gas turbines according to claim 2, wherein the gel comprises: (a) at least two Additives selected from the group consisting of detergents, Dispersants, acids, bases, overbased Detergents, succinylated polyolefins or mixtures thereof, wherein the selected additives form a gel when they to be united; and (b) optionally at least one additive, selected from the group consisting of viscosity modifiers, Friction modifiers, detergents, cloud point depressants, Pour point depressants, demulsifiers, flow improvers, antistatic agents, dispersants, antioxidants, sludge reducing additives, Paint reducing agents, antifoams, corrosion / rust inhibitors, High-pressure / anti-wear agents, seal swelling agents, lubricants, Anti-fogging agents, or mixtures thereof. A lubricant composition for gas turbines according to claim 2 or 3, wherein the gel is a combination of an overbased Detergent and an ashless succinimide dispersant. A lubricant composition for gas turbines according to claim 4, wherein the ratio of detergent to Dispersant is in a range of 10: 1 to 1:10. A lubricant composition for gas turbines according to any one of claims 2-5, wherein the gel is at least an additive selected from the group consisting of viscosity modifiers, Friction modifiers, detergents, cloud point depressants, Pour point depressants, demulsifiers, flow improvers, antistatic agents, dispersants, antioxidants, antifoam agents, Corrosion / rust inhibitors, high pressure / antiwear agents, Seal swelling agents, lubricants, anti-fogging agents, or Mixtures thereof, contains. A lubricant composition for gas turbines according to any one of claims 2-6, wherein the components of the gel at different rates in the first lubricant composition. A method comprising the step of lubricating a Gas turbine with a lubricant composition, said lubricant composition a first lubricant composition and a delivery system, for Delivery of at least one additive to this first lubricant composition in a controlled, delayed manner that involves this first lubricant composition into a second lubricant composition is converted, which is this second lubricant composition different from the first lubricant composition. The method of claim 8, wherein the delivery system includes a gel. The method of claim 9, wherein the gel comprises: (A) at least two additives selected from the group consisting from detergents, dispersants, acids, bases, overbased Detergents, succinylated polyolefins or mixtures thereof, wherein the selected additives form a gel when they to be united; and (b) optionally at least one additive, selected from the group consisting of viscosity modifiers, Friction modifiers, detergents, cloud point depressants, Pour point depressants, demulsifiers, flow improvers, antistatic agents, dispersants, antioxidants, antifoam agents, Corrosion / rust inhibitors, high pressure / antiwear agents, Seal swelling agents, lubricants, anti-fogging agents, or mixtures thereof. The method of claim 9 or 10, wherein said Gel a combination of an overbased detergent and an ashless succinimide dispersant. The method of claim 11, wherein the ratio from detergent to dispersant in the range of 10: 1 to 1:10 lies. The method according to one of the claims 9-12, wherein the gel is at least one additive selected from the group consisting of viscosity modifiers, Friction modifiers, detergents, cloud point depressants, Pour point depressants, demulsifiers, flow improvers, antistatic agents, dispersants, antioxidants, antifoam agents, Corrosion / rust inhibitors, high pressure / antiwear agents, seal swelling agents, Lubricants, antifog agents, or mixtures thereof, contains. The method according to one of the claims 9-13, where the components of the gel with different Dissolve speeds in the first lubricant composition. Gas turbine with the lubricant composition was lubricated according to one of claims 1-7.