CN105623790B - Turbine oil composition and the method for improving steam turbine oil performance - Google Patents

Abstract

The present invention provides a kind of turbine oil composition and the methods for improving steam turbine oil performance.The turbine oil composition of the present invention includes：Alkyl sulfide alcohol ester, demulsifier, antioxidant, extreme pressure anti-wear additives, antirust agent, metal deactivator and major amount of lubricating base oil.The turbine oil composition of the present invention is suitable for the lubrication of Steam Turbine, has excellent wear-resistant and extreme pressure property, inoxidizability, rustless property, anti-foaming property, demulsification performance, divides water quick, thorough, ensures the normal work of steam turbine.

Description

Turbine oil composition and the method for improving steam turbine oil performance

Technical field

It is more particularly to a kind of to be suitable for steam turbine, gas turbine, combustion gas the present invention relates to a kind of turbine oil composition The turbine oil composition of turbine Unit erriger.

Background technology

Gas turbine and steam turbine are one of the important equipments in thermal power plant, and whether normal relation is to electricity for equipment operation The safety problem of power supply.Wherein lubricating oil is to ensure the key component that equipment runs well, and has unit lubrication, the work of cooling With.Due to inevitably contacting water and steam in use so that there are certain moisture in lubricating oil, in addition, profit The applied at elevated temperature under the conditions of existing for air, oil product easily aoxidize and form various oxidation products lubricating oil for a long time, the raising of oil product acid value, Viscosity increases, meanwhile, it is acted on water and air so that point aqueous energy, the antifoam property of oil product decline, and equipment corrosion etc. occur and ask Topic, influences the use of oil product.Wherein, the bearing use temp of gas turbine reaches 120 DEG C, than steam turbine bearing temperature in use High 50 DEG C or so, higher is required for the oxidation stability of oil product.It is therefore desirable to lubricating oil have certain oxidation stability, Anti-foaming property, rust-preventing characteristic, the performance and resistance to emulsion for inhibiting greasy filth generation.Wherein antioxygenic property and resistance to emulsion are two main Index, be related to whether lubricating oil can work normally.

Various lubricating oil have been developed currently on the market, for steam turbine oil and gas turbine oil, such as antioxidant vapour Machine oil, antioxygen rust-preventing characteristic steam turbine oil, anti-ammonia type steam turbine oil, the long-life of combustion gas turbine Unit erriger, anti-general lubricity are taken turns, it is main If in terms of solving the problems, such as the antioxygenic property of lubricating oil and antirust, extreme pressure.

CN101245281《A kind of turbo-engine lube with extreme pressure highly resistance oxidation susceptibility》Providing one kind can meet Extreme pressure property, and the steam turbine oil of antioxygenic property can be met, by 1,3,5 three (3,5- di-t-butyls, 4 hydroxybenzyls) equal three Piperazine, two (2,4- di-tert-butyl phenyl) pentaerythritol bis-phosphites, antimony dialkyl-dithiocarbamate, double focusing isobutene are sub- Amine, 4,4- di-iso-octyldiphenylamines, octyl diphenylamine, 2,6 di-tert-butyl p-cresol, triphenylphosphorothionate, olefine sulfide, fourth Ten di-ammonium salts of base isooctyl phosphoric acid, dodecenylsuccinic acid, benzotriazole octadecylamine salt, the oxozone trimethylene derivative of amine, poly- third Olefin(e) acid ester, base oil composition, have excellent anti-oxidative stability and extreme pressure property, meet special operation condition requirement, have longevity The characteristics of life.

CN102344849《A kind of turbine oil additive composition》A kind of turbine oil additive composition is described, Including C4/C8 alkyl-substituted diphenylamines 8%~30%, N phenyl-α-naphthylamines 6%~12%, phenol type antioxidant 15%~25%, Second, n-butyl dithiocarbamate methyl esters 13%~25%, matal deactivator 8%~10%, extreme pressure anti-wear additives 5%~25%, Antirust agent 3%~20%, demulsifying agent 0.5%~5%.The compositions of additives is free of flux oil, is mixed into base oil Steam turbine oil has excellent oxidation stability, high-temperature stability and liquid phase rust-preventing characteristic, point aqueous energy.

CN102690717《A kind of Extreme-pressure long-life lubricant composition for steam turbine》A kind of extreme pressure long-life steam turbine is provided Lubricant oil composite, the Extreme-pressure long-life lubricant composition for steam turbine contain：Major amount of poly alpha olefin synthetic lubricant fluid base Plinth oil, composite antioxidant, including naphthylamines type antioxidant, alkylated diphenylamine antioxidant, thiophenols ester type antioxidant, can also wrap Include non-essential thioether phenol type antioxidant, matal deactivator, extreme pressure anti-wear additives, ashless anti-rusting additive, demulsifier.The lubricating oil composition Object has excellent oxidation stability, high-temperature stability, extreme pressure property, demulsification performance and liquid phase rustless property.

CN 103113965A《EP turbine oil》A kind of EP turbine oil is disclosed, the steam turbine oil is mainly by base Plinth oil and additive composition, wherein base oil is mainly made of mineral oil, alcohol ester and poly- (alkylidene) glycol, and added with alkyl Diphenylamines and/or phosphite ester, macromolecule shielding phenol, sulphur phosphate, sulfate-phosphate, benzotriazole amine salt, benzotriazole derivative, Oxozone trimethylene derivative, the additive of silicone composite of dodecenylsuccinic acid (ester), amine.The EP turbine oil has There are excellent extreme pressure anti-wear, thermo oxidative stability and greasy filth control, dispersibility, can be good at meeting modern with pole The lubrication needs of the gas turbine of pressure request and large-scale combination circulation steam turbine group.

Although the turbine oil that Yi Shang patent provides has preferable oxidation stability, wear resistence and longer service life, Its performance still has problem, and particularly water-oil separating performance is long there are water-separating time there are problem, divides water is halfway to lack Point affects other performances of turbine oil, and therefore, it is necessary to be further improved.

The content of the invention

The present invention provides a kind of turbine oil composition and the methods for improving steam turbine oil performance.

The turbine oil composition of the present invention, including：Alkyl sulfide alcohol ester, demulsifier, antioxidant, extreme pressure anti-wear additives, antirust Agent, metal deactivator and major amount of lubricating base oil.

The alkyl hydrosulfide and the esterification products of the alkyl carboxylic acid of C2~C20 that the alkyl sulfide alcohol ester is C2~C20, preferably The alkyl hydrosulfide and C2 of the esterification products of the alkyl hydrosulfide of C5~C20 and the alkyl carboxylic acid of C2~C15, most preferably C10~C18~ The esterification products of the alkyl carboxylic acid of C8.When preparing the alkyl sulfide alcohol ester, the alkyl hydrosulfide and C2 of the C2~C20~ The molar ratio of the alkyl carboxylic acid of C20 preferably 1：1~1.02, reaction temperature is 60~120 DEG C, when the reaction time is 2~4 small, two Person occurs to be preferably added to catalyst during esterification, and the addition of the catalyst is the 5%~10% of the two material gross mass, The preferred concentrated sulfuric acid of catalyst.

The alkyl sulfide alcohol ester accounts for the 0.02%~1% of turbine oil composition gross mass, preferably 0.02%~ 0.5%, most preferably 0.02%~0.1%.

The demulsifier is non-polyether class demulsifier and/or polyethers demulsifier.The non-polyether class demulsifier is third The copolymer of olefin(e) acid ester and α-olefin sulfonic acid.

The structure of the copolymer of the acrylate and α-olefin sulfonic acid is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5 ~C10 alkyl or its mixed alkyl；Wherein A1 be hydrogen or methyl, A2 be hydrogen or C1~C4 alkyl, preferably hydrogen, methyl, ethyl or Propyl, most preferably hydrogen, methyl or ethyl, x be 0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is During hydrogen, x is positive integer；M be 1~50 integer, preferably 5~50, most preferably 10~30, n be 1~50 integer, preferably 5~ 50, most preferably 10~20.

The molecular weight of the copolymer of the acrylate and α-olefin sulfonic acid between 1000~15000, preferably 1500~ 10000, most preferably 2000~8000.

The preparation method of the copolymer of the acrylate and α-olefin sulfonic acid is by alkyl acrylate and α-alkenyl sulphur Acid is copolymerized, and collects product.

The structure of the alkyl acrylate is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5 ~C10 alkyl or its mixed alkyl；A1 is hydrogen or methyl.

The alkyl acrylate is to be obtained by methacrylic acid or acrylic acid with alkylol by esterification, and esterification is anti- It is the acidic catalysts such as the concentrated sulfuric acid, acid-exchange resin to answer common catalyst.

The structure of the α-olefin sulfonic acid is：

Wherein A2 is hydrogen or C1~C4 alkyl, and preferably hydrogen, methyl, ethyl or propyl, most preferably hydrogen, methyl or ethyl, x is 0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is hydrogen, x is positive integer.

α-the olefin sulfonic acid is that alpha-olefin and sulfonating agent sulfonating reaction occur and obtains.The alpha-olefin is C3~C10 Alkene, such as the one or more in propylene, butylene, amylene, hexene, heptene, octene, nonene and decene can be selected, preferably C3~C8 alkene, most preferably C3~C6 alkene.The sulfonating agent can select oleum and/or sulfur trioxide.

When sulfonating reaction occurs for alpha-olefin and sulfonating agent, solvent, preferably varsol, the varsol can be added in It is preferred that C5~C10 alkane or its mixture.The 20%~200% of the preferred alpha-olefin quality of addition of the solvent, in sulfonation Solvent is removed after reaction.

The reaction pressure of sulfonating reaction occurs for the alpha-olefin and sulfonating agent preferably between 0.1~4MPa, and most preferably 0.3 ~3.0MPa, reaction temperature is preferably between 0~30 DEG C, and most preferably between 0~20 DEG C, the reaction time preferably 0.1~8 is small When, most preferably 0.3~5 it is small when.

The molar ratio of the alpha-olefin and sulfonating agent preferably 1：1~1.5, more preferable 1：1~1.2.

In the product of the sulfonating reaction alkyl acrylate is cannot participate in containing α-olefin sulfonic acid, sultone, sultone With the copolyreaction of α-olefin sulfonic acid.

Molar ratio between the alkyl acrylate and α-olefin sulfonic acid is 1~50：50~1, preferably 1~10：10~ 1, most preferably 1~3：2~1.

The copolyreaction of the alkyl acrylate and α-olefin sulfonic acid preferably carries out in a solvent, and the solvent is preferably fragrant One or more in hydrocarbon solvent, such as benzene, toluene and dimethylbenzene；Preferably 20~200 DEG C of reaction temperature, more preferable 30~150 DEG C, most preferably 40~120 DEG C, when the time preferably 1~20 of polymerization is small, it is more preferable 2~15 it is small when, most preferably 3~10 it is small when.

The alkyl acrylate and α-olefin sulfonic acid add in initiator when being copolymerized, addition is alkyl acrylate The 0.05%~5% of base ester and α-olefin sulfonic acid gross mass, preferably 0.05%~3%；The preferred azo compound of the initiator And/or peroxide, such as azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, peroxidating bay can be selected Acyl, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, perbenzoic acid uncle Butyl ester, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and mistake Aoxidize the one or more in two dicyclohexyl carbonates, preferably azo diisobutyl and/or benzoyl peroxide, most preferably azo Bis-isobutyronitrile.

Material is washed with water after copolyreaction between the alkyl acrylate and α-olefin sulfonic acid, is removed not The sultone and initiator of reaction；If adding solvent when being copolymerized, removing solvent is needed.

Neutral oil, the neutrality can be added in copolyreaction between the alkyl acrylate and α-olefin sulfonic acid The addition of oil is the 20%~100% of the polymer quality.The neutral oil preferred solvent refined oil and/or poly- α-alkene Hydrocarbon synthetic oil, such as HVI150, No. 6 hydrogenated oils, PAO4, PAO6 can be selected, 100 DEG C of dynamic viscosities of the neutral oil are 1 ~8mm²Between/s.

The polyethers demulsifier is sulfenyl phenolate and propylene oxide, the copolymer of ethylene oxide.

The sulfenyl phenolate and propylene oxide, the structure of copolymer of ethylene oxide are：

Wherein X group isA be 10~100 between integer, preferably 15~80, most It is preferred that 20~60, b are the integer between 5~100, preferably 5~60, most preferably 10~40；K is the integer between 1~10, preferably 1~6, most preferably 1~2；J is the integer between 1~10, and the j on each sulphur bridge can be the same or different, preferably 1~6, Most preferably 1~4；R2 is C1~C18 alkyl or its mixed alkyl, preferably C3~C15 alkyl or its mixed alkyl, most preferably C3~ C10 alkyl or its mixed alkyl.

The sulfenyl phenolate and propylene oxide, the preparation method of copolymer of ethylene oxide include：By sulfenyl phenolate First with Polymerization of Propylene Oxide, again with ethylene oxide polymerization, product is collected.

The sulfenyl phenolate is vulcanization C1~C18 alkyl phenols, preferably vulcanizes C3~C15 alkyl phenols, most preferably vulcanizes C3 ~C12 aligns alkyl phenol；The sulfenyl phenolate is obtained by the reaction by alkyl phenol and vulcanizing agent, and the vulcanizing agent can select sulphur One or more in sulphur, sulfur chloride and sulfur dichloride, the molar ratio of the alkyl phenol and the vulcanizing agent is 1~3：3~1. The temperature of vulcanization is room temperature to 200 DEG C.The sulfur content of sulfenyl phenolate obtained is 5%~20%.

The molar ratio of phenolic hydroxyl group and propylene oxide in the sulfenyl phenolate is 1：10~100, preferably 1：15~80, most It is preferred that 1：20~60；The molar ratio of phenolic hydroxyl group and ethylene oxide in the sulfenyl phenolate is 1：5~100, preferably 1：5~ 60, most preferably 1：10~40.

When preparing the copolymer of the sulfenyl phenolate and propylene oxide, ethylene oxide, solvent is preferably added to, it is described molten Agent preferred aromatic hydrocarbons solvent, most preferably dimethylbenzene and/or toluene, the mass ratio preferably 1 of the sulfenyl phenolate and the solvent： 0.1~50, more preferable 1：0.2~20.

When preparing the copolymer of the sulfenyl phenolate and propylene oxide, ethylene oxide, catalyst is preferably added to, it is described Catalyst preferred alkali metal hydroxide, most preferably potassium hydroxide and/or sodium hydroxide, the sulfenyl phenolate and the catalysis The molar ratio of agent preferably 1：1~20, more preferable 1：1~10, most preferably 1：3~8.

The sulfenyl phenolate and propylene oxide, the reaction pressure of ethylene oxide polymerization are 0.1~1MPa, preferably 0.1~ 0.8MPa, most preferably 0.2~0.6MPa；Reaction temperature be 80 DEG C~200 DEG C, preferably 100 DEG C~160 DEG C, most preferably 120 DEG C~ 140℃；Reaction time for 1~10 it is small when, preferably 2~8 it is small when, most preferably 2~4 it is small when.

The sulfenyl phenolate and propylene oxide, ethylene oxide polymerisation after, 60 are added in into reaction product ~90 DEG C of petroleum ethers, 10% sulfuric acid solution, neutralization reaction product to neutrality after dividing water, drying, add in neutral oil, steam molten Agent obtains sulfenyl phenolate propylene oxide ethylene oxide polymer.

The molecular weight of the sulfenyl phenolate and propylene oxide, the copolymer of ethylene oxide is 1000~30000, preferably 5000~20000, most preferably 10000~20000.

The copolymer of the acrylate and α-olefin sulfonic acid, sulfenyl phenolate propylene oxide ethylene oxide copolymer can be with It is used alone, can also be used in combination；During compound use, mass ratio preferably 1~3 therebetween：3~1.

The demulsifier preferably accounts for the 0.001%~0.1% of turbine oil composition gross mass, most preferably 0.005%~ 0.05%.

The antioxidant is zinc dialkyl dithiophosphate, dialkyl dithiophosphoric acid copper, alkylated diphenylamine, two uncles One or more in butyl paracresol, di-tert-butylphenol, N phenyl-alpha-naphthylamines and sulfenyl phenolate, preferably dialkyl dithio One kind in trbasic zinc phosphate, alkylated diphenylamine, di-tert-butyl p-cresol, di-tert-butylphenol, N phenyl-alpha-naphthylamines and sulfenyl phenolate Or a variety of, most preferably alkylated diphenylamine and/or N phenyl-alpha-naphthylamines.The antioxidant accounts for turbine oil composition gross mass 0.01%~2%, preferably 0.02%~2%, most preferably 0.05%~1%.

The extreme pressure anti-wear additives are the one or more in sulfur-bearing agent, phosphorus containing agent and sulphur phosphorus agent, and the sulfur-bearing agent can be with It selects in sulfide isobutene, vulcanization butylene, vulcanization haco oil, dialkyl dithio amino formate and dibenzyldisulfide One or more, the phosphorus containing agent can select two oleic acid phosphates, dilauryl phosphate, tributyl phosphite ester, two fourths One or more in base phosphite ester, trioctylphosphite, tricresyl alkaliine, the sulphur phosphorus agent can select thio phosphorus Amine acid salt and/or phosphine sulfide hydrochlorate.

The extreme pressure anti-wear additives account for the 0.01%~1% of turbine oil composition gross mass, preferably 0.02%~1%, most It is preferred that 0.05%~0.5%.

The antirust agent is alkenyl succinic acid, barium mahogany sulfonate, dinonyl barium sulfonate, petroleum sodium sulfonate, mahogany acid Calcium, zinc naphthenate, benzotriazole, alkyl imidazoline succinate, oxidized paraffin wax and one kind in Oleate or It is a variety of, preferably alkenyl succinic acid, barium mahogany sulfonate, dinonyl barium sulfonate, alkyl imidazoline succinate, petroleum sodium sulfonate and stone One or more in oily sulfoacid calcium, most preferably alkenyl succinic acid, barium mahogany sulfonate, alkyl imidazoline succinate and dinonyl One or more in barium sulfonate.The antirust agent accounts for the 0.01%~1% of turbine oil composition gross mass, preferably 0.03% ~1%, most preferably 0.03%~0.2%.

The metal deactivator is benzotriazole, bis- mercapto of benzotriazole-aldehyde-amine condensation product, 2-mercaptobenzothiazole and 2,5- Base -1,3, the one or more in 4- thiadiazoles, preferably in benzotriazole, benzotriazole-aldehyde-amine condensation product and 2-mercaptobenzothiazole One or more, most preferably benzotriazole and/or benzotriazole-aldehyde-amine condensation product.The metal deactivator accounts for steam turbine oil group Close the 0.01%~1% of object gross mass, preferably 0.03%~1%, most preferably 0.03%~0.2%.

The lubricating base oil can select the one or more in API I, II, III, IV, V class lubricating base oil, It is preferred that the one or more in API I, II, Group III oil.

The I class oil is the lubricating oil that fraction oil is obtained by clay-filtered, solvent refining, Viscosity Index 80~ Between 100,100 DEG C of dynamic viscosities are in 1~40mm²Between/s；The II class oil is distillate by lube oil hydrogenation Reason obtains, and Viscosity Index is between 100~120, and 100 DEG C of dynamic viscosities are in 1~40mm²Between/s；The Group III oil It is that distillate is obtained by hydroisomerizing, Viscosity Index is more than 120, and 100 DEG C of dynamic viscosities are in 1~40mm²Between/s； The IV classes oil is the synthetic oil of alpha-olefine polymerizing, and Viscosity Index is between 120~150, and 100 DEG C of dynamic viscosities are 1 ~40mm²Between/s；The V classes oil is Synthin oil or Esters oil, and Viscosity Index is between 120~150,100 DEG C dynamic viscosity is in 1~40mm²Between/s, such as adipic acid aliphatic ester, decanedioic acid aliphatic ester, pentaerythritol ester etc..

The present invention also provides it is a kind of improve steam turbine oil performance method, this method be by above-mentioned alkyl sulfide alcohol ester, Demulsifier, antioxidant, extreme pressure anti-wear additives, antirust agent, metal deactivator are added in steam turbine oil.

The turbine oil composition of the present invention is suitable for the lubrication of Steam Turbine film bearing, has excellent wear-resistant and extreme pressure Performance, inoxidizability, rustless property, anti-foaming property, demulsification performance divide water quick, thorough, ensure the normal work of steam turbine oil Make.

Specific embodiment

It further illustrates the present invention rather than limits the invention by the following examples.

Unless stated otherwise, percentage mentioned below is mass percent.

The preparation of 1 tert-dodecylmercaotan capronate of embodiment

With motor agitators and reflux water-dividing, condense the 500mL three-necked flasks of facility, add in 80 grams No. 120 Industrial naptha, tert-dodecylmercaotan 100 grams (M=202.4,0.49mol) then add in 15 gram of 98% concentrated sulfuric acid, and control is anti- Temperature is answered as 90 DEG C, caproic acid 56.9 grams (M=116.2,0.49mol) is added dropwise with separatory funnel, when time for adding is 1 small, then When back flow reaction 3 is small, and the water in reaction is separated, when a point water reaches 8.7 grams (98.6%), stop reaction, cooling separates Then the concentrated sulfuric acid is washed with deionized oil reservoir after neutrality, solvent is evaporated off, obtains 146 grams of oily liquids, As tert-dodecylmercaotan capronate S-1, S content 10.2%.

The preparation of 2 tetradecyl mercaptan propionic ester of embodiment

With motor agitators and reflux water-dividing, condense the 500mL three-necked flasks of facility, add in 60 grams No. 120 Industrial naptha, tetradecyl mercaptan 90 grams (M=230.45,0.39mol) then add in 11 grams of the concentrated sulfuric acid, controlling reaction temperature For 95 DEG C, propionic acid 28.9 grams (M=74,0.39mol) is added dropwise with separatory funnel, when time for adding is 1.2 small, is then refluxed for reacting 4 it is small when, and separate reaction in water, when a point water reaches 6.9 grams (98.3%), stop reaction, cooling, separate water layer, so After oil reservoir is washed with deionized after neutrality, solvent is evaporated off, obtains 111.3 grams of oily liquids, be ten Tetraalkyl mercaptan propionic ester S-2, S content are 11.3%.

The preparation of 3 propene sulfonic acid mixture of embodiment

With stirring, heating, cryostat the corrosion-resistant autoclaves of 500mL in add in 80 grams of 30 DEG C~60 DEG C petroleum ethers, so Rear enclosed reaction kettle opens stirring, and is passed through cryostat and carries out temperature control, then squeezes into 40 grams of propylene into kettle with high-pressure pump (0.952mol), and be passed through high pure nitrogen, control reactor pressure between 0.8~1MPa, control the temperature of reaction kettle 0~ 10 DEG C, the steel cylinder for storing sulfur trioxide is heated, is placed in measuring on electronic scale, then heating temperature is controlled to cause three oxidations Sulphur steel cylinder pressure is more than autoclave pressure, and opens sulfur trioxide steel cylinder outlet valve, and gas is passed through to the snorkel of autoclave In, it then passes to and sulfonating reaction is carried out in the liquid phase of autoclave, sulfur trioxide intake is 77.7 grams (0.971mol), at this time Pressure in reaction kettle is controlled between 0.8~1.2MPa, when the reaction time is 3.2 small, after reaction, to continuously decrease reactor Pressure, after pressure reaches normal pressure, stop stirring, then solvent distillation, obtains 115.8 grams of propene sulfonic acid mixture, analysis It was found that；Containing 54% propene sulfonic acid in the product, 46% propene sultone, the acid value of mixture is 260.8mgKOH/g.

The preparation of 4 butylene azochlorosulfonate acid mixture of embodiment

With stirring, heating, 70 grams of n-hexanes of addition in the 500mL autoclaves of cryostat, then capping kettle, is opened Stirring, and be passed through cryostat and carry out temperature control, butylene 38 grams (0.679mol) is then squeezed into kettle with high-pressure pump, and is passed through High Purity Nitrogen Gas, control reactor pressure control the temperature of reaction kettle that will store sulfur trioxide at 0~10 DEG C between 0.8~1MPa Steel cylinder heats, and is placed in measuring on electronic scale, then controls heating temperature that sulfur trioxide steel cylinder pressure is caused to be more than autoclave pressure Power, and sulfur trioxide steel cylinder outlet valve is opened, gas is passed through in the snorkel of autoclave, then passes to the liquid of autoclave Sulfonating reaction is carried out in phase, sulfur trioxide intake is 54.88 grams (0.686mol), at this time control reaction kettle in pressure 0.8 Between~1.2MPa, when the reaction time is 2.8 small, after reaction, the pressure of reactor is continuously decreased, when pressure reaches normal pressure Afterwards, stirring is stopped, then solvent distillation obtains 91.3 grams of butylene azochlorosulfonate acid mixture, containing 53% butylene sulfonic acid in the product, 47% butene sultone, the acid value of mixture is 225.3mgKOH/g.

The synthesis of 5 acrylic acid C5 ester butylene sulfonic acid copolymers P1 of embodiment

In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70 DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, when polymerisation 1 is small, adds embodiment 4 64 grams of the butylene azochlorosulfonate acid mixture (containing 53% butylene sulfonic acid, 0.25mol, M=136) of preparation, 0.05 gram of two isobutyl of azo Nitrile, be gradually heating to 105 DEG C carry out copolyreaction 4 it is small when.Twice, then reaction product is washed respectively with 200 grams of distilled water 60 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company) are added in, material is warming up to 125 DEG C and is evaporated under reduced pressure, is obtained Acrylic acid C5 ester butylene sulfonic acid copolymer 157.6 grams (P1).Infrared analysis the result shows that：In 1721cm^-1、1160cm^-1Nearby have Strong absworption peak, and illustrate to contain ester type compound in product, 1184cm^-1、1053cm^-1, 3650cm^-1Neighbouring spike shows have Sulfonic acid group exists, 1640cm^-1Nearby non-telescope vibration peak occurs, and does not have double bond presence in compound, illustrates that the compound is Acrylic acid C5 ester butylene sulfonic acid copolymers；Gpc analysis shows the number-average molecular weight of copolymer for 5130, wherein copolymer Content is 61.92%, and the content of flux oil is 38.02%, and the content of acrylic acid C5 esters is 65.47% in copolymer, butylene sulphur The content of acid is 34.53%.

The synthesis of 6 methacrylic acid C8 ester propene sulfonic acids copolymer p 2 of embodiment

In the 500mL three-necked flasks with motor agitators and condenser pipe, 100 grams of dimethylbenzene, 73.6 grams of first are added in Base acrylic acid C8 esters (0.38mol, M=196) add in 0.07 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and rise Temperature is to 75 DEG C, and observing response object has apparent heat release at this time, and controlling reaction temperature is 95 DEG C, when polymerisation 1.5 is small, is added 90.37 grams of propene sulfonic acid mixture (containing 54% propene sulfonic acid, 0.4mol, M=122) prepared by embodiment 3,0.06 gram of idol Nitrogen bis-isobutyronitrile, be gradually heating to 108 DEG C carry out copolyreaction 5 it is small when.Two are washed with 200 grams of distilled water respectively to reaction product It is secondary, 80 grams of 150N (production of Sinopec Shanghai Gaoqiao petrochemical industry branch company) are then added in, material is warming up to 125 DEG C and is depressurized Distillation, obtains methacrylic acid C8 ester propene sulfonic acids copolymer 201 grams (P2).Infrared analysis the result shows that：In 1721cm^-1、 1160cm^-1Nearby there is strong absworption peak, and illustrate to contain ester type compound in product, 1184cm^-1、1053cm^-1、3650cm^-1Place Spike shows with the presence of sulfonic acid group, 1640cm^-1Locate non-telescope vibration peak to occur, there is no double bond presence in compound, illustrate this Compound is methacrylic acid C8 ester propene sulfonic acid copolymers；Gpc analysis shows that the number-average molecular weight of copolymer is 3860, The content of middle copolymer is 60.2%, and the content of flux oil is 39.8%, and the content of methacrylic acid C8 esters is in copolymer 60.83%, the content of propene sulfonic acid is 39.17%.

The synthesis of 7 sulfenyl phenolate A of embodiment

Nonyl phenol 100 grams (0.455mol), 100mL are added in the 500ml three-necked flasks with temperature control and water cooling, stirring N-decane adds in sulphur 35 grams (1.09mol), is then gradually heating to 160 DEG C, and reaction mass is protected with nitrogen, while will be anti- Tail gas is answered to be passed through 10% sodium hydroxide solution, with the hydrogen sulfide gas that absorbing reaction generates, nonyl phenol is by colourless gradual change at this time For dark brown, eventually become black liquor, when reaction 4 is small after, vacuum distillation controlled at 165 DEG C, obtains after steaming desolventizing Sulfenyl phenolate A measures sulfur content as 23.9%.It is measured with VPO methods, the average molecular weight of vulcanization nonyl phenol A is (equivalent for 881 Containing 3 alkyl phenols in each molecule, 3.5) average value of k 1, number of sulfur atoms j is.

The synthesis of 8 sulfenyl phenolate B of embodiment

Dodecylphenol 100 grams (0.382mol) is added in the 500ml three-necked flasks with temperature control and water cooling, stirring, 60~90 DEG C of petroleum ethers of 100ml, controlled at 25~35 DEG C, then be added dropwise sulfur monochloride 36 grams (0.267mol), then by 160 DEG C are gradually warming up to, reaction mass is protected with nitrogen, while reaction end gas is passed through 10% sodium hydroxide solution, it is anti-to absorb The hydrogen chloride gas that should be generated, at this time dodecylphenol gradually become dark brown by colourless, black liquor is eventually become, by 5 It is dripped off after hour, then heats to 100 DEG C, removed solvent, obtain sulfenyl phenolate B, measure sulfur content as 14.7%.Use VPO Method measure, the average molecular weight of vulcanization dodecylphenol B (are converted into each molecule containing 3 alkyl phenols, k 1, sulphur original for 912 2) subnumber j is.

The preparation of 9 sulfenyl phenolate propylene oxide ethylene oxide polymer M1 of embodiment

In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, A3.4 grams of sulfenyl phenolate is added in (0.0039mol contains 0.012mol phenolic hydroxyl groups), 5 grams of dimethylbenzene, 1 gram of solid potassium hydroxide (0.0179mol) then use nitrogen Gas displacement is warming up to 90 DEG C afterwards three times；30 grams of propylene oxide (0.517mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 122 DEG C, when reaction 2.5 is small；Ethylene oxide 12 grams (0.272mol), control are added dropwise into autoclave Reaction pressure 0.5MPa, reaction temperature is 125 DEG C, when reaction 2 is small；It transfers the material into 200ml beakers, adds after reaction Enter 60~90 DEG C of 30 grams of petroleum ethers, 50 milliliters of 10% sulfuric acid solution, remaining potassium hydroxide in neutralization reaction product, and spend Ion water washing, until reaction product is in neutrality；12 grams of HVI150 neutral oils are added in, the oil reservoir in material is put into vacuum distillation Device obtains 53.3 grams of product after steaming solvent, as vulcanizes nonyl phenol propylene oxide ethylene oxide polymer M1, infrared analysis The result shows that 723cm in product^-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm^-1、1249cm^-1Neighbouring peak corresponds to In aromatic ring and the stretching vibration peak of hydroxyl oxygen, in 1060~1150cm^-1Nearby there is the stretching vibration peak of alkyl ehter bond, 2900cm^-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, and the compound for showing generation is sulfenyl phenolate epoxy third Alkane ethylene oxide polymer, determination of elemental analysis sulfur content are 1.56%, and it is 11094 that by gpc analysis, it, which counts equal molecular mass,.

The preparation of 10 sulfenyl phenolate propylene oxide ethylene oxide polymer M2 of embodiment

In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, sulfenyl phenolate B 4.25 is added in Gram (0.00467mol contains 0.014mol phenolic hydroxyl groups), 6 grams of dimethylbenzene, 1.2 grams of solid potassium hydroxides (0.0214mol), then 90 DEG C are warming up to afterwards three times with nitrogen displacement；28 grams of propylene oxide (0.483mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 122 DEG C, when reaction 2.5 is small；Ethylene oxide 17 grams (0.386mol), control are added dropwise into autoclave Reaction pressure 0.5MPa, reaction temperature is 125 DEG C, when reaction 3 is small；It transfers the material into 200ml beakers, adds after reaction Enter 60~90 DEG C of 40 grams of petroleum ethers, add in remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and It is washed with deionized, until reaction product is in neutrality；10 grams of 6# oil is added in, the oil reservoir in material is put into vacuum distillation dress It puts, 58.8 grams of thick liquid is obtained after steaming solvent, as vulcanization dodecylphenol propylene oxide ethylene oxide polymer M2, it is red Outer analysis the result shows that, 723cm in product^-1Neighbouring peak corresponds to the stretching vibration peak of S -- S, 1500cm^-1、1249cm^-1Near Peak corresponds to the stretching vibration peak of aromatic ring and hydroxyl oxygen, in 1060~1150cm^-1Nearby there is the stretching vibration peak of alkyl ehter bond, In 2900cm^-1Neighbouring peak corresponds to methyl and methylene stretching vibration peak, and the compound for showing generation is sulfenyl phenolate epoxy Propane ethylene oxide polymer, determination of elemental analysis sulfur content are 1.06%, and by gpc analysis, its equal molecular mass of number is 10366。

The synthesis of 1 acrylic acid C5 ester acrylic copolymers D1 of comparative example

In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70 DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, when polymerisation 1 is small, adds acrylic acid 18 Gram (0.25mol, M=72), 0.05 gram of azodiisobutyronitrile, be gradually heating to 105 DEG C carry out copolyreaction 4 it is small when.To reaction Product is washed twice respectively with 200 grams of distilled water, then adds in 52 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company), Material is warming up to 125 DEG C to be evaporated under reduced pressure, obtains acrylic acid C5 esters acrylic copolymer 135 grams (D2).Analysis result table It is bright：The number-average molecular weight of copolymer is 4938, and wherein the content of copolymer is 61.48%, and the content of flux oil is 38.52%, The content of acrylic acid C5 esters is 78.02% in copolymer, and the content of acrylic acid is 21.98%.

The synthesis of 2 alkyl phenol propylene oxide ethylene oxide polymer D2 of comparative example

In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, 2.8 grams of nonyl phenol is added in (0.0127mol contains 0.0127mol phenolic hydroxyl groups), 1 gram of solid potassium hydroxide (0.0179mol), then with being risen after nitrogen displacement Temperature is to 92 DEG C；30 grams of propylene oxide (0.517mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 125 DEG C, when reaction 2.5 is small；Ethylene oxide 12 grams (0.272mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, instead Temperature is answered as 125 DEG C, when reaction 2 is small；It transfers the material into after reaction in 200ml beakers, adds in 60~90 DEG C of petroleum ethers 50 grams, remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and be washed with deionized, until anti- Product is answered to be in neutrality；12 grams of HVI150 neutral oils are added in, the oil reservoir in material is put into vacuum distillation apparatus, are obtained after steaming solvent To 55.6 grams of thick liquid, infrared analysis the result shows that, 1500cm^-1、1249cm^-1Neighbouring peak corresponds to aromatic ring and hydroxyl oxygen Stretching vibration peak, 1060~1150cm^-1Between peak correspond to the stretching vibration peak of alkyl ehter bond, in 2900cm^-1Neighbouring peak corresponds to Methyl and methylene stretching vibration peak show that the compound of generation for nonyl phenol propylene oxide ethylene oxide polymer D2, passes through Its equal molecular mass of number of gpc analysis is 3561.

Test method and experiment raw material

1 test method

GB/T265 oil product kinematic viscosity measuring methods and dynamic viscosity calculating method

GB/T2541 oil products viscosity index (VI) calculates table

GB/T3535 petroleum products pour point measuring methods

GB/T12579 lubricating oil spumescence measuring methods

GB/T5096 oil product copper strip test methods

GB/T7305 oil and Synthesis liquid resistance to emulsion pipette method

GB/T11143 inhibitings mineral oil test for rust preventing ability method in the presence of water

GB/T12581 inhibiting mineral oil oxidation characteristic measuring methods

SH/T0306 lubricating oil bearing capacitys measuring method (CL-100 gear mechanisms method)

SH/T0308 lubricating oil air release value measuring methods

2. base oil used in experiment

The base oil of 1 experiment of table

3. test additive therefor

The additive of 2 experiment of table

Additive	Title	Source
			T304	Dibutyl phosphite ester	Shandong Zibo Hui Hua petro-chemical corporations
T306	Tricresyl phosphate	Liaoning Tianhe Fine Chemical Co., Ltd.
			T307	D2EHDTPA amine salt	Nanjing Ning Jiang chemical plant
T321	Sulfide isobutene	Liaoning Tianhe Fine Chemical Co., Ltd.
			T323	Dialkyl dithio amino formate	Liaoning Tianhe Fine Chemical Co., Ltd.
T531	N phenyl αnaphthylamines	Beijing Xing Pu fine chemistry industries company
			T534	Dialkyl diphenylamine	Beijing Xing Pu fine chemistry industries company
T502A	Liquid mixed type shields phenol	Liaoning Tianhe Fine Chemical Co., Ltd.
			T551	Benzotriazole-aldehyde-amine condensation product	Shandong Zibo Hui Hua petro-chemical corporations
T706	Benzotriazole	Shandong Hui Hua petro-chemical corporations
			T746	Alkenyl succinic acid	Lanzhou Lu Borun additives Co., Ltd
T701	Barium mahogany sulfonate	Sinopec Hangzhou Refinery
			T703	17 alkenyl imidazoline succinates	Lanzhou Lu Borun additives Co., Ltd
T1001	Amine and epoxide condensation product	Jinzhou Kangtai Lube Additive Co., Ltd.
			DL-32	Ethylene oxide and propylene oxide copolymers	Wuxi south petroleum additive factory
T901	Poly- methyl-silicone oil	Liaoning Tianhe Fine Chemical Co., Ltd.

HVI150, HVI350 is respectively adopted to be tuned into the base oil of viscosity grade 32,46 (base oil of wherein viscosity 32 is Both HVI150, the base oil of viscosity 46 ratios are 3：2) and embodiment additive and the additive of upper table are modulated into steam turbine The embodiment 11~16 and comparative example additive of fluid composition, the common demulsifier T1001 of upper table additive and lubricating oil, DL32 and anti-foaming agent T901 is modulated into the comparative example 3~8 of lubricant oil composite, and formula composition is shown in Table 3,4.Then performance survey is carried out Examination, and compared with commercially available TSA32 steam turbine oils, result of the test is shown in Table 5,6.

The embodiment of the turbine oil composition of 3 40 DEG C of dynamic viscosities of table 32 and 46

The comparative example of the turbine oil composition of 4 40 DEG C of dynamic viscosities of table 32 and 46

The embodiment performance test of the turbine oil composition of 5 40 DEG C of dynamic viscosities of table 32 and 46

The comparative example performance test of the turbine oil composition of 6 40 DEG C of dynamic viscosities of table 32 and 46

It can be seen from the above result that there is preferable inoxidizability, wear-resistant added with the turbine oil composition of alkyl sulfide alcohol ester Property, added with acrylate olefin sulfonic acid copolymer and/or the steam turbine oil of sulfenyl phenolate propylene oxide ethylene oxide copolymer With preferable demulsibility, and with certain anti-foaming property.And the formula of T1001 and DL32 demulsifiers is used, it breaks Milkiness is not so good as acrylate olefin sulfonic acid copolymer, and when being not added with T901, anti-foaming property is unqualified.Therefore, vapour of the invention Taking turns engine oil base oil has excellent inoxidizability, extreme pressure property, anti-foaming property, rustless property, demulsification performance, can ensure vapour The normal work of turbine.

Claims (19)

1. a kind of turbine oil composition, including：Alkyl sulfide alcohol ester, demulsifier, antioxidant, extreme pressure anti-wear additives, antirust agent, metal Passivator and major amount of lubricating base oil；The demulsifier be non-polyether class demulsifier and/or polyethers demulsifier, it is described Non-polyether class demulsifier is acrylate and the copolymer of α-olefin sulfonic acid, and the polyethers demulsifier is sulfenyl phenolate and ring The copolymer of Ethylene Oxide, ethylene oxide；

The structure of the copolymer of the acrylate and α-olefin sulfonic acid is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl, and A2 is hydrogen or C1~C4 alkyl, and x is 0~4 Integer；When A2 is hydrogen, x is positive integer；M is 1~50 integer, and n is 1~50 integer；

The sulfenyl phenolate and propylene oxide, the structure of copolymer of ethylene oxide are：

Wherein X group is

A is the integer between 10~100, and b is the integer between 5~100；K is the integer between 1~10；

J is the integer between 1~10, and the j on each sulphur bridge can be the same or different；R2 is C1~C18 alkyl or it is mixed Close alkyl.

2. composition described in accordance with the claim 1, which is characterized in that the alkyl sulfide alcohol ester is the alkyl sulfide of C2~C20 The esterification products of the alkyl carboxylic acid of alcohol and C2~C20.

3. composition described in accordance with the claim 1, which is characterized in that it is total that the alkyl sulfide alcohol ester accounts for turbine oil composition The 0.02%~1% of quality.

4. composition described in accordance with the claim 1, which is characterized in that the copolymer of the acrylate and α-olefin sulfonic acid Molecular weight is between 1000~15000.

5. composition described in accordance with the claim 1, which is characterized in that the copolymer of the acrylate and α-olefin sulfonic acid Preparation method is to be copolymerized alkyl acrylate and α-olefin sulfonic acid, collects product；The alkyl acrylate Structure is：

Wherein R1 is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl.

The structure of the α-olefin sulfonic acid is：

Wherein A2 is hydrogen or C1~C4 alkyl, and x is 0~4 integer；When A2 is hydrogen, x is positive integer；

Molar ratio between the alkyl acrylate and α-olefin sulfonic acid is 1~50：50~1；

The alkyl acrylate and α-olefin sulfonic acid add in initiator when being copolymerized.

6. according to the composition described in claim 5, which is characterized in that the copolymerization of the alkyl acrylate and α-olefin sulfonic acid The reaction temperature of reaction is 20~200 DEG C, when the time of polymerization is 1~20 small.

7. composition described in accordance with the claim 1, which is characterized in that the sulfenyl phenolate and propylene oxide, ethylene oxide Copolymer preparation method be by sulfenyl phenolate first with Polymerization of Propylene Oxide, again with ethylene oxide polymerization, collect product.

8. according to the composition described in claim 7, which is characterized in that the sulfenyl phenolate is vulcanization C1~C18 alkyl phenols.

9. according to the composition described in claim 7, which is characterized in that phenolic hydroxyl group and propylene oxide in the sulfenyl phenolate Molar ratio be 1：10~100；The molar ratio of phenolic hydroxyl group and ethylene oxide in the sulfenyl phenolate is 1：5~100.

10. according to the composition described in claim 7, which is characterized in that the sulfenyl phenolate and propylene oxide, ethylene oxide The reaction pressure of polymerization is 0.1~1MPa；Reaction temperature is 80 DEG C~200 DEG C；When reaction time is 1~10 small.

11. composition described in accordance with the claim 1, which is characterized in that the sulfenyl phenolate and propylene oxide, ethylene oxide Copolymer molecular weight be 1000~30000.

12. composition described in accordance with the claim 1, which is characterized in that the demulsifier accounts for turbine oil composition gross mass 0.001%~0.1%.

13. composition described in accordance with the claim 1, which is characterized in that the antioxidant for zinc dialkyl dithiophosphate, Dialkyl dithiophosphoric acid copper, alkylated diphenylamine, di-tert-butyl p-cresol, di-tert-butylphenol, N phenyl-alpha-naphthylamines and vulcanization alkane One or more in base phenol account for the 0.01%~2% of turbine oil composition gross mass.

14. composition described in accordance with the claim 1, which is characterized in that the extreme pressure anti-wear additives for sulfur-bearing agent, phosphorus containing agent and One or more in sulphur phosphorus agent, account for the 0.01%~1% of turbine oil composition gross mass.

15. composition according to claim 14, which is characterized in that the sulfur-bearing agent is selected from sulfide isobutene, vulcanization fourth One or more in alkene, vulcanization haco oil, dialkyl dithio amino formate and dibenzyldisulfide, the phosphorus containing agent Selected from two oleic acid phosphates, dilauryl phosphate, tributyl phosphite ester, dibutyl phosphite ester, trioctylphosphite, One or more in tricresyl alkaliine, the sulphur phosphorus agent are selected from D2EHDTPA amine salt and/or phosphine sulfide hydrochlorate.

16. composition described in accordance with the claim 1, which is characterized in that the antirust agent is alkenyl succinic acid, mahogany acid Barium, dinonyl barium sulfonate, petroleum sodium sulfonate, calcium mahogany sulfonate, zinc naphthenate, benzotriazole, alkyl imidazoline succinate, One or more in oxidized paraffin wax and Oleate account for the 0.01%~1% of turbine oil composition gross mass.

17. composition described in accordance with the claim 1, which is characterized in that the metal deactivator for benzotriazole, benzotriazole- One or more in aldehyde-amine condensation product, 2-mercaptobenzothiazole and 2,5- dimercapto-1,3,4-thiadiazole, account for steam turbine oil The 0.01%~1% of composition gross mass.

18. composition described in accordance with the claim 1, which is characterized in that the lubricating base oil be selected from API I, II, III, One or more in IV, V class lubricating base oil.

19. it is a kind of improve steam turbine oil performance method, be by described in one of claim 1-18 alkyl sulfide alcohol ester, demulsification Agent, antioxidant, extreme pressure anti-wear additives, antirust agent, metal deactivator are added in steam turbine oil.