CN101240212B - Combination circulation steam turbine lubricating oil composition - Google Patents
Combination circulation steam turbine lubricating oil composition Download PDFInfo
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- CN101240212B CN101240212B CN2008101012087A CN200810101208A CN101240212B CN 101240212 B CN101240212 B CN 101240212B CN 2008101012087 A CN2008101012087 A CN 2008101012087A CN 200810101208 A CN200810101208 A CN 200810101208A CN 101240212 B CN101240212 B CN 101240212B
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Abstract
The invention relates to a combined-cycle gas turbine lubricant combination which is suitable to be used in a large-scale gas steam combined-cycle gas turbine, and the composition and content of the combined-cycle gas turbine lubricant combination by weight percentage of antioxidant of 0.1 to 2 percent, anti-wear agent of 0.01 to 1 percent, no gray rust-proof agent of 0.01 to 1 percent, metal deactivating agent of 0.01 to 1 percent, anti-foam agent of 0.001 to 1 percent, the allowance is based oil, which is Class II or Class III paraffin-based oil, and the sulfur content is less than 0.03 percent, the lubricant combination of the invention has an extremely long induction period of oxidation and excellent performance of high temperature oxidation, excellent extreme pressure antifriction property and corrosion, good water separation, air separation and filterability, and can well meet the lubricating demand of large-scale combined cycle gas turbine.
Description
Technical field
The present invention relates to a kind of combination circulation steam turbine lubricating oil composition that is applicable to that large-scale combustion and steam combination circulation steam turbine group is used.
Background technology
The turbine oil that gas-steam combined cycle system is used need satisfy the lubricating requirement of internal combustion turbine and steam turbine simultaneously, and therefore the performance to turbine oil proposes higher requirement.At first, the used lubricating oil of Combined Cycle Unit needs fabulous high temperature oxidation resisting corrosive nature, because the combustion gas initial temperature of internal combustion turbine is more than 1200 ℃, the temperature of its bearing can reach 120 ℃, hot conditions directly influences the oxidation rate of oil product, the continuous increase of the output rating/fuel tank volume of steam turbine simultaneously, promptly the recycle ratio of turbine oil improves constantly, and all requires turbine oil to have the performance of steady running under hot conditions.Secondly, this class lubricating oil need possess good extreme pressure property, to satisfy the lubricating requirement of system's middle gear equipment.For coaxial associating unit, also require oil product have simultaneously outstanding antirust, divide water, anti-bubble and air release property.Domestic turbine oil is in the market produced according to GB11120-89 turbine oil product standard substantially, this standard does not require high temperature oxidation and corrosion performance, the extreme pressure property of oil product, and the most I of employing of domestic turbine oil class base oil produces, and therefore is difficult to satisfy the lubricating requirement of large-scale combination circulation steam turbine group.
In order to improve the oil oxidation stability, just adopt hydrogenated base oil to produce turbine oil since the later stage eighties abroad, hydrogenated base oil saturated hydrocarbon content height (＞90%), very good to the susceptibility of oxidation inhibitor.On the formula technique of oil product, increased the consumption of high temperature amine antioxidants, used amine type oxidation inhibitor comprises the alkyl diphenylamine of C4-C20, as L57, the V961 of Vanderbilt company, the RC 7135 of Rhein company etc. of Ciba company, and phenyl-a-naphthylamine etc.In addition, shield phenol type antioxidant and above alkyl diphenylamine are composite also is the formula technique that adopts usually.Shield phenol type antioxidant commonly used is a 2,6 ditertiary butyl p cresol, 2, the dimer of 6-di-t-butyl-4-alkyl acrylate phenol and this two class formation or the tetramer etc., and used alkyl is the alkyl of C2-C20.The increase oxidation inhibitor especially consumption of alkyl diphenylamine helps prolonging the oxidation induction period of oil product, but also can increase the generation trend of greasy filth simultaneously.The greasy filth that oxidation produces has many harm to the normal operation of Steam Turbine, as the filter screen of greasy filth block pumps suction port, makes pump generation cavitation; Greasy filth is bonded at and makes control that deviation takes place on the control valve, will cause control valve locked when serious; Greasy filth also can be deposited on bearing surface, and its temperature is raise, and causes structure deteriorate.
Summary of the invention
The purpose of this invention is to provide a kind of turbine oil composition with good high-temperature oxidation susceptibility, extreme pressure property and rustless property, said composition can well satisfy the lubrication needs of large-scale combination circulation steam turbine group.
A kind of lubricating oil composition that is used for combination circulation steam turbine, its component and content are by weight percentage: oxidation inhibitor 0.1～2%, anti-wear agent 0.01～1%, Ashless stain-resistant agent 0.01～1%, metal passivator 0.01～1%, kilfoam 0.001～1%, surplus are base oil, and the base oil sulphur content is less than 0.03%.
The component of described lubricating oil composition and content are by weight percentage: oxidation inhibitor 0.5～1.5%, anti-wear agent 0.05～0.5%, Ashless stain-resistant agent 0.05～0.5%, metal passivator 0.03～0.1%, kilfoam 0.003～0.01%, surplus are base oil, base oil is II class or III class paraffin base oil, saturated hydrocarbon content is greater than 90%, and sulphur content is less than 0.03%.
Described oxidation inhibitor is alkyl diphenylamine or alkyl thiodiphenylamine or the two composite mixture, and the ratio of composite mixture is 1: 0.1～10.
Described anti-wear agent is alkylthio phosphoric acid ester, alkyl phosphite, alkyl phosphate amine salt or alkylthio carbamate, and alkyl is the alkyl of C2-C20, comprises butyl, nonyl, decyl or phenyl.
Described Ashless stain-resistant agent is alkenyl succinic acid or phosphate amine salt or the composite mixture of the two, and the ratio of composite mixture is 1: 0.2～10.
Described metal passivator is the methyl benzotriazole derivative.
Lubricating oil composition provided by the invention, its oxidation inhibitor adopts alkyl diphenylamine or alkyl thiodiphenylamine or the two composite mixture, and the ratio of composite mixture is 1: 0.1～10.Studies show that the composite use of alkyl thiodiphenylamine and alkyl diphenylamine can significantly improve the oxidation susceptibility of oil product.Used alkyl diphenylamine comprises octyl diphenylamine, nonyl diphenylamine, styroyl pentanoic, butyl octyl pentanoic or octyl group styroyl pentanoic.Used alkyl thiodiphenylamine comprises butyl thiodiphenylamine, octyl group thiodiphenylamine, styroyl thiodiphenylamine, nonyl thiodiphenylamine or butyl octyl thiodiphenylamine and octyl group thiodiphenylamine dimer.The oxidation inhibitor consumption is 0.1～2% of the total metering of composition, preferably 0.5～1.5%.
Because the extreme pressure property of lubricating oil and the improvement of rustless property are conflicting, the improvement of extreme pressure property can have influence on rustless property, otherwise the improvement of rustless property can influence again to extreme pressure property, therefore, need between extreme pressure anti-wear additives and rust-preventive agent, realize fine equilibrium.Used extreme pressure anti-wear additives is ashless among the present invention, had better not cause adverse influence to oxidation susceptibility, has suitable activity, and unsuitable excessive, otherwise can cause the corrosive problem.Extreme pressure anti-wear additives comprises alkylthio phosphoric acid ester, alkyl phosphite, alkyl phosphate amine salt or alkylthio carbamate, and alkyl is the alkyl of C2-C20, comprises alkyl such as butyl, nonyl, decyl or phenyl.The anti-wear agent consumption is 0.01～1% of the total metering of composition, preferably 0.05～0.5%.
Rust-preventive agent is ashless, and acid number is unsuitable too high, selects alkenyl succinic acid or phosphate amine salt or the composite mixture of the two for use, and the ratio of composite mixture is 1: 0.2～10.The rust-preventive agent consumption is 0.01～1% of the total metering of composition, preferably 0.05～0.5%.
The chain reaction of hydro carbons can be caused in the metallic surface, and the metal ion of trace is Cu especially
2+And Fe
3+, the oxidation of hydro carbons is played katalysis.Add metal passivator in the lubricating oil, can suppress the katalysis of metal ion oxidation.The used metal passivator of the present invention is the methyl benzotriazole derivative, and consumption is 0.01～1% of the total metering of composition, preferably 0.03～0.1%.
Lubricating oil composition provided by the present invention does not limit the use of kilfoam, and consumption is 0.001～1% of the total metering of composition.Used kilfoam is methylsiloxane mixture or liquid ester multipolymer.
Lubricating oil composition provided by the invention has following characteristics: 1, outstanding pyro-oxidation resistance, rotary oxygen bomb reaches 1600 minutes, the TOST oxidation life-span was greater than 20000 hours, hot metal corrosion test (ASTM D4636,175 ℃ of * 3h) medium viscosity increases less than 5%, and acid number increases less than 0.5mgKOH/g; 2, outstanding extreme pressure property, FZG is greater than 11 grades; 3, outstanding rust-preventing characteristic, water separable performance, air separation and filterableness; 4, lower acid number, the acid number of processed oil is not more than 0.2mgKOH/g.To sum up, said composition can satisfy the lubrication needs of large-scale combination circulation steam turbine group well.
Embodiment
By composition preparation full formula lubricating oil listed in the following table, used base oil is II class or III class paraffin base oil, and saturated hydrocarbon content is greater than 90%, and sulphur content is less than 0.03%.
Embodiment 1
| Component | Content (weight percent %) |
| Butyl octyl-pentanoic butyl octyl-thiodiphenylamine alkylthio carbamate alkyl phosphate amine salt alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 1 0.1 0.2 0.1 0.02 0.03 0.002 surpluses |
Embodiment 2
| Component | Content (weight percent %) |
| Butyl octyl-pentanoic butyl octyl-thiodiphenylamine dialkyl dithiophosphate alkyl phosphorous acid ester methyl benzotriazole derivative methylsiloxane kilfoam | 0.5 0.2 0.05 0.5 0.07 0.003 |
| Base oil | Surplus |
Embodiment 3
| Component | Content (weight percent %) |
| Butyl octyl-pentanoic butyl octyl-thiodiphenylamine dialkyl dithiophosphate alkylthio carbamate alkyl phosphate amine salt alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.4 0.1 0.1 0.4 0.05 0.05 0.1 0.001 surpluses |
Embodiment 4
| Component | Content (weight percent %) |
| Butyl octyl-pentanoic butyl octyl-thiodiphenylamine alkyl phosphate amine salt methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.6 0.6 0.3 0.05 0.005 surpluses |
Embodiment 5
| Component | Content (weight percent %) |
| Butyl octyl-pentanoic butyl octyl-thiodiphenylamine alkyl phosphorous acid ester | 0.5 1 0.3 |
| Alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.1 0.05 0.004 surplus |
Embodiment 6
| Component | Content (weight percent %) |
| Butyl octyl-pentanoic butyl octyl-thiodiphenylamine dialkyl dithiophosphate alkyl phosphorous acid ester alkyl phosphate amine salt alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.2 1.8 0.2 0.1 0.01 0.05 0.05 0.006 surpluses |
Embodiment 7
| Component | Content (weight percent %) |
| Nonyl diphenylamine butyl-thiodiphenylamine dialkyl dithiophosphate alkyl phosphate amine salt alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.9 0.1 0.03 0.2 0.03 0.03 0.002 surpluses |
Embodiment 8
| Component | Content (weight percent %) |
| Nonyl diphenylamine butyl-thiodiphenylamine alkyl phosphorous acid ester alkylthio carbamate alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.5 0.25 0.5 0.05 0.1 0.07 0.003 surplus |
Embodiment 9
| Component | Content (weight percent %) |
| Nonyl diphenylamine butyl-thiodiphenylamine dialkyl dithiophosphate alkyl phosphate amine salt alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.2 0.8 0.1 0.1 0.03 0.1 0.001 surpluses |
Embodiment 10
| Component | Content (weight percent %) |
| Nonyl diphenylamine nonyl-thiodiphenylamine alkyl phosphorous acid ester | 0.6 0.6 0.4 |
| Alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.07 0.05 0.005 surplus |
Embodiment 11
| Component | Content (weight percent %) |
| Nonyl diphenylamine nonyl-thiodiphenylamine dialkyl dithiophosphate alkylthio carbamate alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 1.5 0.3 0.08 0.2 0.06 0.05 0.004 surpluses |
Embodiment 12
| Component | Content (weight percent %) |
| Nonyl diphenylamine nonyl-thiodiphenylamine alkyl phosphorous acid ester alkyl phosphate amine salt alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.3 1.5 0.3 0.05 0.05 0.05 0.006 surpluses |
Embodiment 13
| Component | Content (weight percent %) |
| Styroyl pentanoic butyl-thiodiphenylamine dialkyl dithiophosphate alkylthio carbamate alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 1 0.1 0.15 0.1 0.1 0.03 0.002 surpluses |
Embodiment 14
| Component | Content (weight percent %) |
| Styroyl pentanoic butyl-thiodiphenylamine alkyl phosphorous acid ester alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.5 1.2 0.2 0.1 0.07 0.003 surpluses |
Embodiment 15
| Component | Content (weight percent %) |
| Styroyl pentanoic butyl octyl-thiodiphenylamine alkyl phosphate amine salt methyl benzotriazole derivative methylsiloxane kilfoam | 0.4 0.9 0.3 0.1 0.001 |
| Base oil | Surplus |
Embodiment 16
| Component | Content (weight percent %) |
| Styroyl pentanoic styroyl-thiodiphenylamine alkyl phosphorous acid ester alkylthio carbamate alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.8 0.7 0.1 0.3 0.08 0.05 0.005 surpluses |
Embodiment 17
| Component | Content (weight percent %) |
| Styroyl pentanoic octyl group-thiodiphenylamine dimer alkylthio carbamate alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.2 0.6 0.5 0.1 0.05 0.004 surpluses |
Embodiment 18
| Component | Content (weight percent %) |
| Styroyl pentanoic octyl group-thiodiphenylamine dimer | 0.2 1.6 |
| Alkyl phosphorous acid ester alkylthio carbamate alkyl phosphate amine salt alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 0.05 0.4 0.07 0.03 0.05 0.006 surpluses |
Embodiment 19
| Component | Content (weight percent %) |
| Butyl octyl-pentanoic octyl group-thiodiphenylamine dimer alkyl phosphorous acid ester alkenyl succinic acid methyl benzotriazole derivative methylsiloxane kilfoam base oil | 1.2 0.5 0.2 0.1 0.07 0.003 surpluses |
Claims (8)
1. combination circulation steam turbine lubricating oil composition, it is characterized in that: its component and content are by weight percentage: oxidation inhibitor 0.1～2%, anti-wear agent 0.01～1%, Ashless stain-resistant agent 0.01～1%, metal passivator 0.01～1%, kilfoam 0.001～1% and base oil are surplus;
Base oil be saturated hydrocarbon content greater than 90%, sulphur content is less than 0.03% paraffin base oil;
Oxidation inhibitor is that alkyl diphenylamine is or/and the alkyl thiodiphenylamine;
Anti-wear agent is alkylthio phosphoric acid ester, alkyl phosphite, alkyl phosphate amine salt or alkylthio carbamate;
The Ashless stain-resistant agent is that alkenyl succinic acid is or/and phosphate amine salt;
Metal passivator is the methyl benzotriazole derivative;
Kilfoam is methylsiloxane mixture or liquid ester multipolymer.
2. a kind of combination circulation steam turbine lubricating oil composition according to claim 1 is characterized in that: component and content are by weight percentage: oxidation inhibitor 0.5～1.5%, anti-wear agent 0.05～0.5%, Ashless stain-resistant agent 0.05～0.5%, metal passivator 0.03～0.1%, kilfoam 0.003～0.01%, surplus are base oil.
3. a kind of combination circulation steam turbine lubricating oil composition according to claim 1 is characterized in that: oxidation inhibitor alkyl diphenylamine and the composite mixture of alkyl thiodiphenylamine are 1 by weight: (0.1～10).
4. a kind of combination circulation steam turbine lubricating oil composition according to claim 1 is characterized in that: the alkyl of anti-wear agent alkylthio phosphoric acid ester, alkyl phosphite, alkyl phosphate amine salt or alkylthio carbamate is the alkyl of C2-C20.
5. a kind of combination circulation steam turbine lubricating oil composition according to claim 4 is characterized in that: the alkyl of anti-wear agent alkylthio phosphoric acid ester, alkyl phosphite, alkyl phosphate amine salt or alkylthio carbamate is that the alkyl of C2-C20 is butyl, nonyl or decyl.
6. a kind of combination circulation steam turbine lubricating oil composition according to claim 1 is characterized in that: the weight ratio of the composite mixture of Ashless stain-resistant agent alkenyl succinic acid and phosphate amine salt is 1: 0.2～10.
7. a kind of combination circulation steam turbine lubricating oil composition according to claim 1 is characterized in that: alkyl diphenylamine is octyl diphenylamine, nonyl diphenylamine or butyl octyl pentanoic.
8. a kind of combination circulation steam turbine lubricating oil composition according to claim 1 is characterized in that: the alkyl thiodiphenylamine is butyl thiodiphenylamine, octyl group thiodiphenylamine or nonyl thiodiphenylamine.
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| CN2008101012087A CN101240212B (en) | 2008-02-29 | 2008-02-29 | Combination circulation steam turbine lubricating oil composition |
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| CN2008101012087A CN101240212B (en) | 2008-02-29 | 2008-02-29 | Combination circulation steam turbine lubricating oil composition |
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| CN101240212B true CN101240212B (en) | 2010-07-28 |
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| CN102676279A (en) * | 2011-03-10 | 2012-09-19 | 中国石油天然气股份有限公司 | Ship steam turbine lubricating oil composition |
| CN102690703B (en) * | 2011-03-24 | 2014-10-29 | 中国石油化工股份有限公司 | Extreme-pressure long-life industrial lubricant composition |
| CN102690717B (en) * | 2011-03-24 | 2014-08-20 | 中国石油化工股份有限公司 | Extreme-pressure long-life lubricant composition for steam turbine |
| CN103319536A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Phosphorothioate-containing thiadiazole type additive preparation method |
| CN102746923A (en) * | 2012-07-10 | 2012-10-24 | 上海福岛化工科技发展有限公司 | Steam turbine oil |
| CN103571577B (en) * | 2012-07-31 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of steam turbine lubricating oil composition |
| CN105623794B (en) * | 2014-11-04 | 2018-09-04 | 中国石油天然气股份有限公司 | A kind of gas turbine additive composition for lubricant oil |
| CN105713701B (en) * | 2014-12-05 | 2018-10-16 | 中国石油天然气股份有限公司 | Compositions of additives for steam turbine lubricating oil |
| CN105733761A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Steam turbine lubricating oil composition |
| CN104927988A (en) * | 2015-06-01 | 2015-09-23 | 杭州万润能源科技有限公司 | Dedicated engine oil formulation for industrial engine running-in |
| EP3380594B1 (en) * | 2015-11-24 | 2021-10-06 | Shell Internationale Research Maatschappij B.V. | Use of an additive for improving the air release of a lubricating oil |
| CN112239694A (en) * | 2019-07-17 | 2021-01-19 | 中国石油化工股份有限公司 | Turbine oil composition and use thereof |
| CN112646637A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Turbine oil composition, preparation method and application thereof |
| CN112646643A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Turbine oil composition for ships, preparation method and application thereof |
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