EP0978554A2 - Huiles de turbine ou R&O comprenant des inhibiteurs de rouille neutre - Google Patents

Huiles de turbine ou R&O comprenant des inhibiteurs de rouille neutre Download PDF

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Publication number
EP0978554A2
EP0978554A2 EP99305884A EP99305884A EP0978554A2 EP 0978554 A2 EP0978554 A2 EP 0978554A2 EP 99305884 A EP99305884 A EP 99305884A EP 99305884 A EP99305884 A EP 99305884A EP 0978554 A2 EP0978554 A2 EP 0978554A2
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Prior art keywords
base oil
oils
turbine
carbon atoms
oil
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EP99305884A
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German (de)
English (en)
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EP0978554B1 (fr
EP0978554A3 (fr
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David Kenvyn Walters
Helen Theresa Ryan
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Afton Chemical Ltd
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Afton Chemical Ltd
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    • C10M169/00Lubricating 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
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Definitions

  • the present invention relates to turbine and rust and oxidation (R&O) oils (hereinafter “turbine oils”) having improved wet filterability without detriment to hydrolytic stability.
  • turbine oils turbine and rust and oxidation oils
  • Steam and gas turbine oils are top-quality rust- and oxidation-inhibited oils.
  • Steam turbines employ steam that enters the turbine at high temperature and pressure and expands across both rotating and fixed blades. Only the highest-quality lubricants are able to withstand the wet conditions, high temperatures and long periods of service associated with steam turbine operation. In gas turbines, they must withstand contact with very hot surfaces, often with intermittent operation and periods of nonuse. Therefore, to be effective, both types of oil must have, in addition to good corrosion protection and demulsibility, outstanding resistance to oxidation, which includes a minimum tendency to form deposits in critical areas of the system.
  • a finished turbine oil will contain only the base oil, antioxidants, rust inhibitors, demulsifiers, corrosion inhibitors and diluents, if necessary.
  • Prior art turbine oils contain acidic rust inhibitors.
  • acidic rust inhibitors of the type taught in U.S. Patent No. 4,101,429, have been used in turbine oils.
  • turbine oils containing acidic rust inhibitors exhibit satisfactory rust performance, they tend to interact with, for example, water and metal detergents present as contaminants producing particulates, precipitates and/or sludge.
  • Acidic rust inhibitors thus create problems with deposit formation and filterability upon exposure to contaminants such as water and/or metal detergents. The resulting filterability problems and deposit formation are expensive and highly undesirable.
  • the present invention provides a composition suitable for use as a turbine or rust and oxidation (R & O) oil comprising a major portion of a base oil and (A) at least one neutral rust inhibitor, wherein the base oil has a viscosity index of greater than 80, a saturates content of greater than 90 wt% and a sulfur content of 0.5 wt% or less.
  • R & O turbine or rust and oxidation
  • neutral rust inhibitors in the present specification, means rust inhibitors that are essentially free of a -COOH functional group.
  • major portion means that the composition contains at least 50% by weight base oil.
  • a combination of neutral rust inhibitor(s) and a compound (B) of formula: in which Z is a group R 1 R 2 CH-, in which R 1 and R 2 are each independently hydrocarbon groups containing from 1 to 34 carbon atoms, the total number of carbon atoms in the groups R 1 and R 2 being from 11 to 35, are added to the base oil in order to provide a turbine oil which ensures good rust performance, good wet filterability and good performance in thermal stability tests where water and/or metal detergents are present, e.g. the ASTM D 2619 and ASTM D 4310 tests.
  • hydrocarbyl groups and moieties may be straight- or branched-chain.
  • turbine oils are produced which are substantially free of acidic rust inhibitors and/or metal detergents.
  • substantially free means that no acidic rust inhibitors or metal detergents are purposefully added to the finished oil although there may be some present due to contamination or as an impurity.
  • the at least one neutral rust inhibitor is a hydrocarbyl ester of formula R (COOR') n , in which R and R' are each independently hydrocarbyl groups, or hydroxyhydrocarbyl groups, containing upto about 40 carbon atoms, preferably 8 to 20 carbon atoms, and n is from 1 to about 4.
  • R and R' are each independently hydrocarbyl groups, or hydroxyhydrocarbyl groups, containing upto about 40 carbon atoms, preferably 8 to 20 carbon atoms, and n is from 1 to about 4.
  • the maximum number of groups COOR' which are present on the hydrocarbyl or hydroxyhydrocarbyl group R will vary depending on the number of carbon atoms in R. For example, if R is a hydrocarbyl group containing only one carbon atom, the maximum possible value of n will be 4. When R is a hydroxyhydrocarbyl group containing one carbon atom the maximum value of n will be 3.
  • the hydrocarbyl esters can be prepared by conventional esterification procedures from a suitable alcohol and an acid, acid halide, acid anhydride or mixtures thereof.
  • the esters of the invention can be prepared by conventional methods of transesterification.
  • essentially free it is meant that the starting acids, acid halides, acid anhydrides or mixtures thereof used in preparing the neutral rust inhibitors are reacted with an amount of alcohol sufficient to theoretically convert all of the -COOH groups to esters.
  • the neutral rust inhibitor will have a TAN of less than 10mgKOH/g.
  • Preferred esters include, but are not limited to, octyloleyl malate, dioleylmalate, pentaerythritol monooleate and glycerol monooleate.
  • Another class of preferred neutral rust inhibitors includes aspartic acid diesters of 1-(2-hydroxyethyl)-2-heptadecenyl imidazoline.
  • This imidazoline is primarily a mixture of diester of L-aspartic acid and an imidazoline based on the reaction between oleic acid and aminoethanolamine.
  • Esters of this type are commercially available from Mona Industries, Inc. as Monacor® 39.
  • the radical Z may be, for example, 1-methylpentadecyl, 1-propyltridecenyl, 1-pentyltridecenyl, 1-tridecenylpentadecenyl or 1-tetradecyleicosenyl.
  • the number of carbon atoms in the groups R 1 and R 2 is from 16 to 28 and more commonly 18 to 24. It is especially preferred that the total number of carbon atoms in R 1 and R 2 is about 20 to 22.
  • the preferred compound (B) is 3-C 18-24 alkenyl-2,5-pyrrolidindione, i.e. a compound in which the average number of carbon atoms in the alkenyl group is from 18 to 24.
  • the compound (B) has a titratable acid number (TAN) of about 80 to about 140 mgKOH/g, preferably about 110mgKOH/g.
  • TAN titratable acid number
  • the compounds (B) are commercially available or may be made by the application or adaptation of known techniques (see for example EP-A-0389237).
  • Lubricating oils contemplated for use in this invention include natural lubricating oils, synthetic lubricating oils and mixtures thereof. Suitable lubricating oils also include basestocks obtained by isomerization of synthetic wax and slack wax, as well as basestocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of crude oil.
  • both the natural and synthetic lubricating oils will each have a kinematic viscosity ranging from about 1 x 10 -6 m 2 /s to about 40 x 10 -6 m 2 /s (about 1 to about 40 cSt) at 100o C, although typical applications will require each oil to have a viscosity ranging from about 2 x 10 -6 m 2 /s to about 8 x 10 -6 m 2 /s (about 2 to about 8 cSt) at 100o C.
  • Natural base oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.
  • the preferred natural base oil is mineral oil.
  • the mineral oils useful in this invention include all common mineral oil base stocks. This would include oils that are naphthenic or paraffinic in chemical structure. Oils that are refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulfur dioxide, furfural, dichlordiethyl ether, etc. They may be hydrotreated or hydro-refined, dewaxed by chilling or catalytic dewaxing processes, or hydrocracked. The mineral oil may be produced from natural crude sources or be composed of isomerized wax materials or residues of other refining processes.
  • the mineral oils will have kinematic viscosities of from 2 x 10 -6 m 2 /s to 12 x 10 -6 m 2 /s (2 cSt to 12 cSt) at 100°C.
  • the preferred mineral oils have kinematic viscosities of from 3 x 10 -6 m 2 /s to 10 x 10 -6 m 2 /s (3 to 10 cSt), and most preferred are those mineral oils with viscosities of 5 x 10 -6 m 2 /s to 9 x 10 -6 m 2 /s (5 to 9 cSt) at 100°C.
  • Synthetic lubricating oils useful in this invention include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized, and interpolymerized olefins [e.g., polybutylenes, polypropylenes, propylene, isobutylene copolymers, chlorinated polylactenes, poly(1-hexenes), poly(1-octenes), and mixtures thereof]; alkylbenzenes [e.g., polybutylenes, polypropylenes, propylene, isobutylene copolymers, chlorinated polylactenes, poly(1-hexenes), poly (1-octenes) and mixtures thereof]; alkylbenzenes [e.g., dodecylbenzenes, tetradecylbenzenes, dinonyl-benzenes and di(2-ethylhexyl)benzene]; polyphenyl
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by esterification or etherification.
  • This class of synthetic oils is exemplified by: polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polypropylene glycol having a molecular weight of 100-1500); and mono- and poly-carboxylic esters thereof (e.g., the acetic acid esters, mixed C 3 -C 8 fatty acid esters, and C 12 oxo acid diester of tetraethylene glycol).
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids and alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers and propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, lino
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isophthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid.
  • a preferred type of oil from this class of synthetic oils are adipates of C 4 to C 12 alcohols.
  • Esters useful as synthetic lubricating oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. These oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(dimethyl)-siloxanes and poly (methylphenyl) siloxanes.
  • oils include tetra-ethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethyl
  • Other synthetic lubricating oils include liquid esters of phosphorus containing acids (e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid), polymeric tetra-hydrofurans and poly- ⁇ -olefins.
  • liquid esters of phosphorus containing acids e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid
  • polymeric tetra-hydrofurans e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid
  • polymeric tetra-hydrofurans e.g., polymeric tetra-hydrofurans and poly- ⁇ -olefins.
  • the lubricating base oils may be derived from refined, re-refined oils, or mixtures thereof.
  • Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
  • Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
  • Re-refined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques for removal of spent additives and oils breakdown products.
  • White oils, as taught in U.S. 5,736,490 may also be used as the base oil for the turbine and R&O oil.
  • the base oils have a viscosity index (VI) of greater than 80, a saturates content of greater than 90 wt% and sulfur content of 0.5 wt% or less. In a preferred embodiment the oils have a sulfur content of 0.3 wt% or less, more preferably 0.1 wt% or less.
  • the preferred base oils for use in the present invention are the hydroprocessed and/or iso-dewaxed mineral oil, synthetic oils and mixtures thereof.
  • the turbine and R&O oils of the present invention may be prepared by simple blending of the various components with a suitable base oil.
  • the additive component(s) used in practice of this invention may be provided as a concentrate for formulation into a turbine or R&O oil ready for use.
  • Concentrates of the present invention, containing neutral rust inhibitor(s), but no compound (B), are typically added to the base oil at a treat rate of about 0.5 to about 2%, for example about 0.7 to about 2%, by weight based on the weight of the finished oil.
  • Concentrates of the present invention containing both neutral rust inhibitor(s) and compound (B) tend to impart greater rust protection in the presence of sea water (ASTM D665B) and are typically added to the base oil at a treat rate of from about 0.2 to about 2%, for example, about 0.3 to about 2%, by weight based on the weight of the finished oil.
  • the neutral rust inhibitor(s) When used, without the addition of compound (B), they are generally present in the additive concentrate in an amount of from about 10 to about 60 percent by weight, based on the total weight of the concentrate. When used in combination with compound (B), the neutral rust inhibitor(s) are generally present in the additive concentrate in an amount of from 10 to 60 percent by weight, based on the total weight of the concentrate, while compound (B) is generally present in the additive concentrate in an amount of from about 1 to 15 percent by weight.
  • the concentrate may comprise, in addition to the fluid components, a solvent or diluent for the fluid components. The solvent or diluent should be miscible with and/or capable of dissolving in the turbine base oil to which the concentrate is to be added.
  • Suitable solvents and diluents are well known.
  • the solvent or diluent may be the turbine base oil itself.
  • the concentrate may suitably include any of the conventional additives used in turbine oils. The proportions of each component of the concentrate are controlled by the intended degree of dilution, though top treatment of the formulated fluid is possible.
  • the neutral rust inhibitor(s) should be present in the finished oil in an amount of at least about 0.10, and preferably from 0.10 to about 0.45 percent by weight.
  • compound (B) if used, should be present in the finished oil in an amount of about 0.008 to about 0.25 percent by weight.
  • the additive concentrates and finished oils of the present invention may further contain additional additives such as phosphorus-containing additives and sulfurized esters.
  • additional additives such as phosphorus-containing additives and sulfurized esters.
  • Preferred phosphorus containing additives include amine salts of acid phosphates and phosphorus and sulfur containing compounds.
  • additives commonly used in turbine and R&O oils may be included in the turbine and R&O oils of the present invention. These include antioxidants, demulsifiers and corrosion inhibitors. These additives, when present, are used in amounts conventionally used in turbine oil packages.
  • Turbine Oil Concentrates 1-4 represent formulations within the scope of the present invention, i.e., they contain neutral rust inhibitors and are substantially free of acidic rust inhibitor.
  • Turbine Oil Concentrate 5 represents an additive concentrate outside of the scope of the present invention in that it contains an acidic rust inhibitor. All of the samples used similar conventional additives (e.g., antioxidants, demulsifiers and corrosion inhibitors) in similar amounts.
  • Turbine Oil Concentrates Turbine Oil 1 (TO1) Turbine Oil 2 (TO2) Turbine Oil 3 (TO3) Turbine Oil 4 (TO4) Turbine Oil 5 (TO5) (Comparative) Rust Inhibitor V 21.25 Rust Inhibitor W 0.50 Rust Inhibitor X 22.50 22.50 Rust Inhibitor Y 20.00 Rust Inhibitor Z 12.00 Compound B 5.00
  • Turbine oils are prepared by adding additive concentrates as described above to base oils of various viscosities at a treat rate of 0.8 percent by weight.
  • the base oil used was a hydro-processed (HP) mineral oils having a VI of at least 98, a saturates level of at least 98% and a sulfur content of less than 0.01 wt%.
  • a solvent refined (SR) base oil was also used.
  • the finished oils were tested for wet filterability using the Shell Filtration Test and for rust performance using the ASTM D 665B rust test.
  • the Shell Filtration Test is intended to evaluate the filterability characteristics of oil based hydraulic fluids with and without calcium and/or water contamination.
  • the fluids as blended and the contaminated fluids are each tested in duplicate as follows. After pre-treatment at 70 °C, 300 ml of test oil are filtered through a 1.2 micron Millipore membrane using a 650 mm Hg vacuum. The fluid temperature is not controlled but should be in the range of 19 to 26 °C. The times for each successive 100 ml of fluid to filter, or for the filter membrane to block, are noted. In the following Tables the results of the Shell Filtration Test are indicated as either PASS, meaning that all 300 ml of oil passed through the filter, or FAIL, meaning that the filter became blocked.
  • Shell Filtration Test results Additive Concentrate Base Oil - ISO # Shell Filtration Test D665B rust test TO4 HP - 32 PASS PASS TO5 SR - 32 FAIL PASS TO5 SR - 46 FAIL PASS TO4 HP - 68 PASS PASS TO5 SR - 68 FAIL PASS TO4 HP - 100 PASS PASS
  • compositions of the present invention exhibit both passing Shell Filtration results and ASTM D 665B results. Further, it is clear from the above Table 2 that turbine oils (TO5) containing sufficient amounts of acidic rust inhibitor to pass the ASTM D 665B rust test fail the Shell Filtration Test.
  • turbine oils In handling, i.e., storing and transporting, of turbine oils, the turbine oil often comes into contact with residual lubricating fluids containing acidic rust inhibitors and/or metal detergents or turbine oils containing acidic rust inhibitors.
  • the turbine oils of the present invention enable passing Shell Filtration Test results upon contamination with these sources of acidic rust inhibitors and/or metal detergents.
  • Turbine oils containing components (A) and (B) of the present invention have been found to exhibit excellent thermal stability in tests with water present and passing rust test performance.
  • ASTM D 4310 is used to determine the tendency of inhibited mineral oils, especially turbine oils, to form sludge during oxidation in the presence of oxygen, water, and copper and iron metals at an elevated temperature.
  • an oil sample is reacted with oxygen in the presence of water and an iron-copper catalyst coil for 1000 hours. The oil is then analysed to determine the total acid number (TAN), the weight of sludge and loss of copper and iron from the catalyst.
  • Table 3 shows the hydrolytic stability in the presence of water of turbine oils containing the combination of additives (A) and (B) of the present invention.
  • the formulated oil included pentaerythritol monooleate at a concentration of 0.18 wt % and 3-C 18-24 alkenyl-2,5-pyrrolidindione at a concentration of 0.04 wt%.
  • the base oil was a hydro-processed basestock having a viscosity index of 99, a saturates content of 99.5 wt % and a sulfur content of 0.02 wt %.
  • Sludge (mg) Copper wt. change (mg) Iron wt. change (mg) TAN (mg/KOH g) 12.5 0.5 0.75 0.425
  • the results represent the average of 2 runs.
  • the additive combinations of the present invention are especially effective in hydro-processed mineral oils.
  • Table 4 demonstrates the exceptional properties of the additive systems of the present invention in these hydro-processed mineral oils.
  • the following formulated oils contained identical additive concentrates (TO4).
  • the solvent refined mineral oils (SR-32 and SR-68) contained 0.82 wt% of TO4, while the hydro-processed mineral oils (HP-32, HP-68 and HP-100) contained 0.80 wt% of TO4.
  • the formulated oils were tested in the Rotating Bomb Oxidation Test (RBOT) defined in ASTM D-2272.
  • the RBOT is a test for estimating the oxidation stability of turbine oils.
  • test oil, water and copper catalyst coil contained in a covered glass container, are placed in a bomb equipped with a recording pressure gauge.
  • the bomb is charged with oxygen to a pressure of 620 kPa, placed in a constant-temperature oil bath set at 150 °C, and rotated axially at 100 rpm at an angle of 30° from the horizontal.
  • the number of minutes required to reach a specific drop in gauge pressure is the oxidation stability of the test sample.
  • the formulated oils containing solvent refined basestocks were also tested in the Lifetime Turbine Oil Oxidation Test (Life TOST) as defined in ASTM D-943.
  • the Life TOST is used to evaluate the oxidation stability of inhibited steam turbine oils.
  • the oil sample is reacted with oxygen in the presence of water and an iron-copper catalyst at 95 °C. The test continues until the measured total acid number of the oil is 2.0 mg KOH/g.
  • the number of test hours required for the oil to reach 2.0 mg KOH/g is the "oxidation lifetime".
  • the RBOT for base oil alone would be in the region of 15-30 minutes.
  • Base oil RBOT (minutes) Life TOST (hours) SR-32 602.5 6188 (avg. of 2 runs) HP-32 1199 (avg. of 3 runs) SR-68 707.5 6032 (avg. of 2 runs) HP-68 1292 (avg. of 3 runs) HP-100 1253 (avg. of 3 runs)

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
EP99305884A 1998-08-04 1999-07-26 Huiles de turbine ou R&O comprenant des inhibiteurs de rouille neutre Expired - Lifetime EP0978554B1 (fr)

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GBGB9816951.9A GB9816951D0 (en) 1998-08-04 1998-08-04 Turbine and R&O oils containing neutral rust inhibitors
GB9816951 1998-08-04

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6645920B1 (en) 2002-11-14 2003-11-11 The Lubrizol Corporation Additive composition for industrial fluid
WO2008031808A2 (fr) * 2006-09-11 2008-03-20 Showa Shell Sekiyu K.K. Composition pour huile lubrifiante
WO2008074760A1 (fr) * 2006-12-19 2008-06-26 Shell Internationale Research Maatschappij B.V. Composition d'huile lubrifiante comprenant un ester époxydé et un dérivé d'acide aspartique
US11988657B2 (en) 2018-09-19 2024-05-21 Mitsubishi Heavy Industries, Ltd. Method for determining degree of sludge generation in oil

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100387696C (zh) * 2005-12-29 2008-05-14 上海交通大学 苯并三氮唑多硫化物极压抗腐蚀添加剂及其制备方法
JP5838679B2 (ja) * 2011-09-13 2016-01-06 東レ・ファインケミカル株式会社 洗浄液
CN111575088A (zh) * 2019-02-19 2020-08-25 中国石油天然气股份有限公司 一种防锈剂组合物
CN114276853A (zh) * 2021-12-29 2022-04-05 中海油气(泰州)石化有限公司 一种高过滤性多用途蒸汽轮机油复合添加剂组合物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2971912A (en) * 1956-05-14 1961-02-14 Castrol Ltd Lubricating oil compositions
US4101429A (en) * 1977-07-21 1978-07-18 Shell Oil Company Lubricant compositions
EP0259809A2 (fr) * 1986-09-08 1988-03-16 Idemitsu Kosan Company Limited Composition d'huile lubrifiante
EP0393732A2 (fr) * 1989-04-21 1990-10-24 King Industries, Inc. Compositions thermo-oxydativement stables
US5089157A (en) * 1991-03-18 1992-02-18 Nalco Chemical Company Hot melt lubricant having good washability
EP0776964A1 (fr) * 1995-12-01 1997-06-04 Ethyl Petroleum Additives Limited Fluides hydrauliques
EP0799883A1 (fr) * 1995-10-19 1997-10-08 Idemitsu Kosan Company Limited Composition d'huile hydraulique

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3401349B2 (ja) * 1994-12-07 2003-04-28 新日本石油株式会社 潤滑油組成物
CN1045469C (zh) * 1996-07-25 1999-10-06 中国石油化工总公司 一种润滑油降凝剂

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2971912A (en) * 1956-05-14 1961-02-14 Castrol Ltd Lubricating oil compositions
US4101429A (en) * 1977-07-21 1978-07-18 Shell Oil Company Lubricant compositions
EP0259809A2 (fr) * 1986-09-08 1988-03-16 Idemitsu Kosan Company Limited Composition d'huile lubrifiante
EP0393732A2 (fr) * 1989-04-21 1990-10-24 King Industries, Inc. Compositions thermo-oxydativement stables
US5089157A (en) * 1991-03-18 1992-02-18 Nalco Chemical Company Hot melt lubricant having good washability
EP0799883A1 (fr) * 1995-10-19 1997-10-08 Idemitsu Kosan Company Limited Composition d'huile hydraulique
EP0776964A1 (fr) * 1995-12-01 1997-06-04 Ethyl Petroleum Additives Limited Fluides hydrauliques

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6645920B1 (en) 2002-11-14 2003-11-11 The Lubrizol Corporation Additive composition for industrial fluid
WO2008031808A2 (fr) * 2006-09-11 2008-03-20 Showa Shell Sekiyu K.K. Composition pour huile lubrifiante
WO2008031808A3 (fr) * 2006-09-11 2008-07-31 Shell Int Research Composition pour huile lubrifiante
WO2008074760A1 (fr) * 2006-12-19 2008-06-26 Shell Internationale Research Maatschappij B.V. Composition d'huile lubrifiante comprenant un ester époxydé et un dérivé d'acide aspartique
US11988657B2 (en) 2018-09-19 2024-05-21 Mitsubishi Heavy Industries, Ltd. Method for determining degree of sludge generation in oil

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Publication number Publication date
EP0978554B1 (fr) 2003-12-17
CN1100858C (zh) 2003-02-05
CN1244571A (zh) 2000-02-16
DE69913615T2 (de) 2004-10-14
SG85123A1 (en) 2001-12-19
CA2276920A1 (fr) 2000-02-04
JP3642556B2 (ja) 2005-04-27
DE69913615D1 (de) 2004-01-29
GB9816951D0 (en) 1998-09-30
JP2000063879A (ja) 2000-02-29
EP0978554A3 (fr) 2000-03-08
KR20000017030A (ko) 2000-03-25

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