CN102477340B - Lubricant composition for internal combustion engines - Google Patents
Lubricant composition for internal combustion engines Download PDFInfo
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Abstract
A lubricant composition for internal combustion engines is provided, which comprises a lubricant base oil and a sulfonate detergent, wherein the content of the sulfonate detergent is 0.8% to 1.5% (by weight) calculated on the basis of the composition; the sulfonate detergent comprises calcium sulfonate with a ultra-high base number more than 400 mg KOH/g, calcium sulfonate with a high base number of 300 to 350 mg KOH/g and lithium sulfonate with a base number less than 150 mg KOH/g. The lubricant composition has low contents of S, P and sulfuric ash, the additives used have a low cost and are easily available, and the economical efficiency is better. The lubricant composition can not only meet the requirements for normal operation of engines but also meet the requirements for normal operation of automobile exhaust gas recirculation (EGR) systems.
Description
Technical field
The present invention is lubricant composition for internal combustion engines, specifically, is a kind of lubricating oil composition for petrol motor and diesel engine.
Background technology
Along with the increase of China's automobile quantity, motor vehicle exhaust becomes the principal element of contaminate environment, contains the material of the severe contamination air such as carbon monoxide, hydro carbons and oxynitride in tail gas.Therefore vehicle exhaust is filtered, is absorbed processing very necessary.The method of processing at present vehicle exhaust is that the three-way catalyst in convertor is oxidized to carbonic acid gas and water by the carbon monoxide in tail gas and hydrocarbon compound by the tail gas convertor is installed, and reduction of nitrogen oxide is nitrogen and oxygen.
Three-way catalyst is very responsive for the sulphur in engine oil, phosphorus and ash content.The too high meeting of sulphur content causes engine inner acidic material to increase, and too high sulfated ash can form particle and be adsorbed on particulate filter, and further assembles the backpressure rising that causes particle trapper, causes exhaust gas recirculation in engine, the fuel consumption aggravation.The too high meeting of phosphorus content makes the three-way catalyst poisoning and deactivation in particle trapper.Therefore, the sulphur, phosphorus content and the ash content that reduce in engine oil are one of developing direction from now on.
At present in the low-sulfur of exploitation, low-phosphorous and low ash content automobile engine lubricating oil composition, mainly contain alkylsalicylate etc. without sulfur additives, because alkylsalicylate has excellent high temperature detergency, in formula, can meet with less dosage various performance requriementss.
CN1493671A discloses the diesel engine oil lubricating oil composition lower than 50ppm fuel for sulphur content, wherein uses at least one metal detergent, and metal detergent produces total ashes lower than 1.0wt%.Contain at least one alkylsalicylate in purification agent.MackT-10 tests demonstration, and its lead corrosion result is better.
CN1746279A discloses a kind of lubricating oil composition, and wherein sulphur content is less than 0.3wt%, and phosphorus content is less than 0.08wt%, and ash content is less than 0.8wt%, contains the salicylate fatty acid additive in formula.
CN1746280A discloses a kind of low-sulfur, low-phosphorous and low-ash lubricating oil composition, wherein sulphur content is less than 0.3wt%, phosphorus content is less than 0.08wt%, ash content is less than 0.8wt%, used the additive of boracic and the alkylsalicylate that total basicnumber is 200～400mgKOH/g in formula, wherein the mass ratio of the nitrogen in ashless dispersant and boron is 3～5: 1.Composition has the effect that reduces lubricating oil viscosity and improve the piston detergency.
The base number of the disclosed lubricating oil composition of CN1754950A is 8～9mgKOH/g, and sulphur content is less than 0.3wt%, and phosphorus content is less than 0.08wt%, and ash content is less than 0.8wt%, the nitrogenous dispersion agent that contains high alkalinity magnesium salts purification agent and 2.5～4%.
CN1782047A discloses the lubricating oil composition that a kind of sulfated ash is less than 1%, comprising lubricant base, the alkyl sodium salicylate purification agent, at least magnesium salts of 200ppm and low-molecular-weight ashless dispersant, said composition can reduce the wearing and tearing of engine piston apical ring in MackT-10.
CN1782048A discloses the lubricating oil composition that a kind of sulfated ash is less than 1%, comprising lubricant base, the alkyl sodium salicylate purification agent, at least the high alkalinity magnesium sanitising agent of 200ppm and at least molybdenum compound of the oil soluble sulfur-bearing of the molybdenum of 20ppm, be at least lubricating oil the nitrogenous dispersion agent of 0.09% nitrogen is provided, said composition can reduce the wearing and tearing of engine piston apical ring in oil engine.
USP6569818 discloses a kind of lubricating oil composition, composition contains 0.01～0.3% sulphur, 0.01～0.1% phosphorus, 0.1～1% sulfated ash, 0.2～7% metal-salt, wherein the sulphur content of base oil is less than 0.1%, 0.01～0.3% ashless dispersant (in nitrogen atom content), metal detergent is selected from the basic metal of the unvulcanised that base number is 10～350mgKOH/g or the alkylsalicylate of alkaline-earth metal, or basic metal or the alkaline earth salt of the alkylphenol derivative with its (Mannich) alkali structure of Manny of unvulcanised, 0.01～0.1% dialkyl dithio zinc, 0.01～5% be selected from the antioxidant that contains amine and phenolic compound.
The disclosed lubricating oil composition of USP7563752 mainly comprises: 0.005～0.2% basic metal or alkaline-earth metal alkylsalicylate, and 0.005～0.2% phosphorous anti-wear agent, 0.01～1% amides, in composition, total sulfur content is 0.3%.
Research is found, adopts alkylsalicylate and over base sulfosalt, phenates combination in formula, then with other additive compound, can make the high temperature detergency of lubricating oil composition improve, guarantee to meet other requirement simultaneously.
CN101108995A discloses phosphorus content and has been less than 0.12%, sulphur content is less than 0.4%, the lubricating oil composition that sulfated ash is less than 1.0%, total basicnumber approximately 7～15, comprise main amount base oil, minor amount high alkalinity magnesium purification agent and at least 0.5wt% be selected from phenolic antioxidant without sulphur, containing the ashless oxidation inhibitor of amine oxidation inhibitor and their mixture, high alkalinity magnesium purification agent is greater than 60% for the contribution of total Base Number Analyses of Lubricants.Composition has oxidation-resistance and resistance to abrasion preferably.
CN1183237C discloses a kind of phosphorus content lower than 0.1% large diesel engine lubricating oil composition, mixture comprising ashless dispersant, neutral calcium phenylate, oil soluble high alkaline calcium sulfonate and overbased magnesium sulphonates, zinc dialkyl dithiophosphate and ashless antioxidant, said composition has high temperature detergency, resistance to abrasion and anti-oxidative stability preferably.
USP6730638 discloses the engine starts oil lubricating oil of low ash content, low-phosphorous, low-sulfur, base oil by the sulphur content 300ppm of main amount, 0.5～10% boracic ashless dispersant, 0.05～1.5% the friction improver containing molybdenum, 0.05 at least one of～5.0% be selected from sulfonate, alkylphenol or salicylate metal detergent, 0.1～0.75% thiophosphoric acid zinc, the wherein purification agent of the preferred alkaline including earth metal of purification agent.
USP5958848 discloses a kind of low chlorine, low-ash crankcase lubricating oil composition, at least contain 1.5% chloride ashless dispersant and purification agent system, the purification agent system comprises sulfonate and is selected from alkylphenol, a kind of phenates of sulfenyl phenolate and alkyl salicylate, described phenates provides at least phenolic hydroxyl group of 0.0025g, wherein sulfonate or metal-salt are high alkalinity salt, comprise the carbonate that is no more than 0.008g, the gram equivalent ratio of phenolic hydroxyl group salt and sulfonate is 1.4: 1, total organic metal salt is 0.5: 1 with the ratio of carbonate, lubricating oil composition cl content 50ppm, sulfated ash 1.2%, at least comprise a kind of oil-soluble magnesium salts in metal detergent.
CN101108994A discloses a kind of lubricating oil composition, wherein phosphorus content is less than 0.9%, sulphur content is less than 0.3%, sulfated ash is less than 1.0%, the ashless dispersant that adopts heat " alkene " reaction to make, high alkaline calcium sulfonate is as purification agent unique in lubricating oil, and the raw materials such as olefin copolymer vi modifiers prepare lubricating oil composition, and composition has oxidation-resistance, resistance to abrasion and high temperature detergency preferably.
USP5486300 discloses a kind of lubricating oil composition, mainly comprise lubricant base, at least one high alkalinity organic acid alkali metal salt, mainly high alkalinity sulfonate sodium or sylvite, its amount is at least to contain an alkali metal salt of 0.005 equivalent in every 100g oil, a kind of dispersion agent that wherein metal of high alkalinity salt ratio is 3～40, at least 1.13%, at least one dialkyl dithiophosphate.This patent is not determined sulphur content, the concrete numerical value of phosphorus content and sulfated ash.
USP6596672 discloses the low ash content lubricating oil composition that contains multiple high alkaline detergent and antioxidant, comprise: lubricant base, 0.01 the overbased calcium of～0.79% sulfated ash, magnesium, barium, strontium salt, 0.01～0.79% high alkalinity magnesium salts or sodium salt, 0.1 the shielding phenolic antioxidant of～1.5% thiazolinyl coupling, 0.1 at least one arylamine antioxidant of～6%, shielding phenol and arylamine content are at least 0.5%, lubricating oil composition sulfated ash 0.1～0.8%.
The prior art demonstration, the employing alkylsalicylate is metal detergent, can meet on the basis of properties, the consumption of metal additive in the reduction system, meet oil product low-sulfur, low-phosphorous and low-ash requirement.But alkylsalicylate preparation process complexity, product cost is high.
With sulfonic acid calcium salt and the composite modulation lubricating oil composition of alkylsalicylate, although combine the advantage of the two, in the storage of oil product and use procedure, additive easily becomes turbid or precipitates, and affects its further use.
Generally to introduce the additives such as a small amount of high alkalinity sulfonic acid magnesium, high alkalinity sodium sulfonate or high alkalinity potassium sulfonate in the composition that the calcium sulfonate with high base number of take is metal detergent, the introducing of high alkalinity magnesium salts affects to the high temperature detergency of composition, and the introducing of high alkalinity sodium sulfonate or potassium can make the resistance to abrasion of lubricating oil composition descend, simultaneously, limitation due to high alkalinity sodium sulfonate or sylvite antioxidation property, need to introduce more antioxidant, make the economy of formula be affected.
Summary of the invention
The purpose of this invention is to provide a kind of lubricant composition for internal combustion engines, this lubricating oil composition, when guaranteeing to have preferably high temperature detergency, oxidation-resistance, resistance to abrasion and base number retentivity, has lower sulphur, p and s hydrochlorate ash oontent.
Lubricant composition for internal combustion engines provided by the invention, comprise lubricant base and sulfonate detergent, wherein the content of sulfonate detergent take composition as benchmark be 0.8～1.5 quality %, described sulfonate detergent comprises that base number is greater than the overbased calcium sulphonate of 400mgKOH/g, and the calcium sulfonate with high base number that base number is 300～350mgKOH/g and base number are lower than the Sulfonic Lithium of 150mgKOH/g.
The present invention selects three kinds of sulfonate detergents with different base numbers to combine sulfonate detergent, and do not adopt the alkylsalicylate purification agent, for antifriction and the abrasion resistance that further improves lubricating oil composition, select the friction improver and the above-mentioned sulfonate detergent that contain the ester class composite, again with other additive, as antioxidant, ashless dispersant, viscosity index improver and pour point depressant and base oil are modulated into lubricating oil composition, said composition has high temperature detergency preferably, anti-oxidative stability, antifriction antiwear and base number retentivity, and sulphur, phosphorus content is low.The present invention's additive cost used is lower, be easy to obtain, and has economy preferably, and the lubricating oil composition of preparation, when meeting engine work, also can meet the normal operation of vehicle tail gas circulation (EGR) system.
Embodiment
Lubricating oil composition of the present invention comprises lubricant base and three kinds of sulfonate detergents with different base numbers, use these three kinds of sulfonate can meet the requirement of high temperature detergency, deacidification and the base number retentivity of lubricating oil composition, can reduce the usage quantity of metal additive simultaneously, thereby reduce ash content, sulphur and the phosphorus content of lubricating oil composition.For making composition reach the use properties requirement of lubricating oil, preferably add friction improver and other additive of containing the ester class.
Described three kinds of Sulfonic Lithiums that the sulfonate detergent with different base numbers is overbased calcium sulphonate, calcium sulfonate with high base number and low alkali value.The base number of described overbased calcium sulphonate is 400～500mgKOH/g preferably, and the base number of calcium sulfonate with high base number is 300～330mgKOH/g preferably, and the base number of Sulfonic Lithium is 50～180mgKOH/g preferably.
The mass ratio of described overbased calcium sulphonate, calcium sulfonate with high base number and Sulfonic Lithium is 1: 2～3: 1～2.
For improving the antifriction anti-friction of lubricating oil composition, preferably by sulfonate detergent of the present invention and the friction improver assembly that contains ester group functional group, therefore, preferably, also comprise 0.1～0.4 quality %, the preferred friction improver that contains ester group functional group of 0.15～0.3 quality % in described lubricating oil composition.
The described friction improver that contains ester group functional group is by C
10～C
40alkyl carboxylic acid or thiazolinyl carboxylic acid and C
2～C
5alcohol make through esterification, described alcohol can be monohydroxy-alcohol, dibasic alcohol or trivalent alcohol.The preferred C of described friction improver
16～C
24alkyl carboxylic acid glycol ester, butyl stearate, oleic acid diethyl alcohol ester or olein.
In sulfonate detergent, contained sulfonic acid is alkyl benzene sulphonate (ABS) or mahogany acid, and sulfonate is synthetic by sulfonic acid.On the phenyl ring of described alkyl benzene sulphonate (ABS) or mahogany acid, one or more alkyl substituent can be arranged, the alkyl that substituting group is straight or branched, total carbon number of substituted alkyl on benzene ring is 10～30, preferably 12～28.
For making lubricating oil composition reach the performance index of regulation, in composition, also should contain appropriate ashless dispersant, oxidation inhibitor, tackifier and pour point depressant.Preferably, also comprise the nitrogenous ashless dispersant of 1.0～3.0 quality %, the oxidation inhibitor of 0.5～1.5 quality %, the viscosity index improver of 5～10 quality % and the pour point depressant of 0.1～1.0 quality % in composition.
The preferred polyisobutene succinimide type of described nitrogenous ashless dispersant dispersion agent, its molecular weight preferably 1000～3000.This dispersion agent is by polyisobutene and maleic anhydride hydrocarbonylation, and and containing the compound of amine for example the polyamines polyene amination reaction make.Dispersion agent can be single, double or many Ashless butyl diimide dispersants.Ashless dispersant in lubricating oil effectively the jelly of barrier carbon distribution mutually assemble, prevent that it is deposited on metallic surface.
The preferred zinc dialkyl dithiophosphate of described oxidation inhibitor, its synthetic method is: first by alcohol and P
2s
5reaction generates dialkyl dithiophosphoric acid, then reaction generates zinc dialkyl dithiophosphate with zinc oxide, and described alkyl can be C
4straight chained alkyl, C
8straight chained alkyl, can be also C
4the isomery alkyl.Select the zinc salt of different alkyl according to the job requirement of lubricating oil composition.The Main Function of zinc dialkyl dithiophosphate is the superoxide formed in decomposition reaction, suppresses oil oxidation.
The ethylene-propylene copolymer that described viscosity index improver preferred number average molecular weight is 50000～100000.Preferred 40～60 quality % of ethylene content in ethylene-propylene copolymer, propylene content is 60～40 quality % preferably.Use viscosity index improver to regulate lubricating oil viscosity, can improve the working efficiency of oil engine, fuel economy.
The preferred C of described pour point depressant
8～C
12alpha-olefin polymers, by C
8～C
12alpha-olefin polymerization obtain.Pour point depressant can be adsorbed on the wax in oil product, and the reticulated structure of wax while destroying low temperature guarantees that oil product can flow when low temperature.
Present composition base oil used is mainly hydro carbons lubricating oil, can be I class oil, II class oil, III class oil, can be also IV class oil, can be also above several mixture, base oil mainly meets the viscosity requirement of lubricating oil composition, and 100 ℃ of viscosity of lubricant base are 3～20mm
2/ s, preferably 9～17mm
2/ s.The selection of base oil also will be considered other performance requriements of composition, as Nock vaporization losses and viscosity index etc.
Lubricating oil composition provided by the invention is mainly used in the lubricated of petrol motor and diesel engine.
Further describe the present invention below by example, but the present invention is not limited to this.
The method of evaluating performance of the composition prepared in example is as follows:
High temperature detergency:
Carry out lacquering and the experiment of coking plate on L-1 plate-type coking device.Coking: plate temperature/oil temperature=320 ℃/100 ℃, time 2 h, stop/ETAD expected time of arrival and departure=45 seconds/15 seconds.Lacquering: plate temperature/oil temperature=300 ℃/150 ℃, time 2 h, continuously.
On L-A type detergency tester, tested, to investigate its high temperature detergency.Plate temperature/oil temperature=300 ℃/100 ℃, 1 hour time, stop/ETAD expected time of arrival and departure=40 seconds/20 seconds.Oil droplet speed 1.0ml/min.
Anti-oxidative stability:
Measure with the TA5000DSC2910 thermal analyzer, investigate the thermal oxidation stability of oil product by PDSC (Pressure Differential Scanning Calorimeter pressure means of differential scanning calorimetry) method.
Rupture of oil film load and frictional coefficient:
The anti-wear and wear-resistant performance evaluation of GB/T3142-82 lubricant.
Wear scar diameter:
SH/T 0189 lubrication oil antiwear damages performance measurement method (four-ball tester method).
The base number retentivity:
The 200ml test tube, during 150 ℃ of oil temperatures, pass into air, and Ventilation Rate 10ml/min measures base number and changes after 2 hours.
Example 1～3
Prepare composition of the present invention.
By 150SN, 500SN, 150BS is modulated into base oil by the mass ratio of 14: 5: 1, and 100 ℃ of viscosity are 14.5mm
2/ s, its performance meets the requirement of 15W/40 base oil.
Sulfonate detergent, friction improver, antioxidant, ashless dispersant, viscosity index improver and pour point depressant are added in the base oil modulated and make lubricating oil composition, and additive title and the index of use are as follows:
Sulfonate detergent:
Overbased calcium sulphonate: base number 405mgKOH/g, calcium contents 14.5 quality %, sulphur content 1.43 quality %.
Calcium sulfonate with high base number: base number 311mgKOH/g, calcium contents 10.2 quality %, sulphur content 1.8 quality %.
Low alkali value Sulfonic Lithium: base number 135mgKOH/g, lithium content 1.91 quality %, sulphur content 2.07 quality %.
Friction improver:
The dimeracid glycol ester, the synthetic C of 1014 dimeracids of employing Emery company
18the alkyl carboxylic acid glycol ester, acid number is 26mgKOH/g.
Oleic acid diethyl alcohol ester, acid number is 38mgKOH/g.
Antioxidant:
Zinc dialkyl dithiophosphate (T202), zinc content 8.2 quality %, sulphur content 15.1 quality %, phosphorus content 8.2 quality %, in composition, content is 0.9 quality %.
Ashless dispersant:
Mono butonediimide (T151), nitrogen content 2.1 quality %, base number is 50mgKOH/g, in composition, content is 1.5 quality %.
Viscosity index improver (T613):
Ethylene-propylene copolymer, molecular weight Mn is 85000, ethylene content 51 quality %, propylene content 49 quality %, ethylene-propylene copolymer content in composition is 7.0 quality %.
Pour point depressant (T803):
Alpha-olefinic polymer, the Mn molecular weight is 2352, in composition, content is 0.3 quality %.
Each example sulfonate detergent used, the content of friction improver in composition is in Table 1, the sulphur of composition, phosphorus content, and detergency, oxidation-resistance, antifriction and resistance to abrasion and base number retentivity evaluation result are in Table 2.
Comparative Examples 1～5
Press the method compositions formulated of example 1, different is that the purification agent added is different with friction improver, each Comparative Examples sulfonate detergent used, the content of friction improver in composition are in Table 1, the sulphur of composition, phosphorus content, detergency, oxidation-resistance, antifriction and resistance to abrasion and base number retentivity evaluation result are in Table 2.
The base number of the overbased magnesium sulfonate adopted in Comparative Examples is 402mgKOH/g, Mg content 9.3 quality %, and sulphur content 1.42 quality %,
The base number of sulfonate with high base number sodium is 407mgKOH/g, sodium content 17.0 quality %, sulphur content 1.53 quality %.
Table 1
Table 2
From table 2 data, the lubricating oil composition sulfated ash of the present invention's preparation is less than 0.8 quality %, phosphorus content is less than 0.08 quality %, sulphur content is less than 0.2 quality %, have excellent high temperature detergency, anti-oxidative stability, antifriction antiwear and base number retentivity, the composition antifriction antiwear of example 1 preparation that does not wherein add friction improver is slightly poor.The composition of Comparative Examples 1 preparation does not adopt Sulfonic Lithium as purification agent, and high temperature detergency is poor, and the composition of Comparative Examples 2 preparations does not adopt overbased calcium sulphonate, and the base number retentivity descends very fast.The composition of Comparative Examples 3 preparations is owing to only adopting overbased calcium sulphonate, and its high temperature detergency is poor.The composition of Comparative Examples 4 preparations adopts overbased magnesium sulfonate to replace Sulfonic Lithium, and its high temperature detergency is poor, and the composition of Comparative Examples 5 preparations adopts sulfonate with high base number sodium to replace Sulfonic Lithium, and high temperature detergency and anti-oxidative stability are poor, and the sulfated ash maximum.
Claims (9)
1. a lubricant composition for internal combustion engines, comprise lubricant base and take the sulfonate detergent that content that composition is benchmark is 0.8～1.5 quality %, 0.15 the friction improver that contains ester group functional group of～0.3 quality %, described sulfonate detergent comprises that base number is greater than the overbased calcium sulphonate of 400mgKOH/g, the calcium sulfonate with high base number that base number is 300～350mgKOH/g and base number are lower than the Sulfonic Lithium of 150mgKOH/g, described overbased calcium sulphonate, the mass ratio of calcium sulfonate with high base number and Sulfonic Lithium is 1: 2～3: 1～2, described friction improver is C
16～C
24alkyl carboxylic acid glycol ester, butyl stearate, oleic acid diethyl alcohol ester or olein.
2. according to composition claimed in claim 1, it is characterized in that sulfonic acid used in sulfonate detergent is alkyl benzene sulphonate (ABS) or mahogany acid.
3. according to composition claimed in claim 2, the total carbon number that it is characterized in that the substituted alkyl on benzene ring of alkyl benzene sulphonate (ABS) is 10～40.
4. according to composition claimed in claim 1, it is characterized in that in composition also comprising the nitrogenous ashless dispersant of 1.0～3.0 quality %, the oxidation inhibitor of 0.5～1.5 quality %, the viscosity index improver of 5～10 quality % and the pour point depressant of 0.1～1.0 quality %.
5. according to composition claimed in claim 4, it is characterized in that described nitrogenous ashless dispersant is polyisobutene succinimide type dispersion agent.
6. according to composition claimed in claim 4, it is characterized in that described oxidation inhibitor is zinc dialkyl dithiophosphate.
7. according to composition claimed in claim 4, it is characterized in that described viscosity index improver is the ethylene-propylene copolymer that number-average molecular weight is 50000～100000.
8. according to composition claimed in claim 4, it is characterized in that described pour point depressant is C
8～C
12alpha-olefin polymers.
9. according to composition claimed in claim 1, it is characterized in that 100 ℃ of viscosity of lubricant base are 3～20mm
2/ s.
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| WO2015076417A1 (en) * | 2013-11-25 | 2015-05-28 | 出光興産株式会社 | Lubricating oil composition for spark-ignition internal combustion engine |
| CN105524681B (en) * | 2014-10-23 | 2019-10-29 | 中国石油化工股份有限公司 | A kind of gasoline engine oil friction improver and its application |
| CN104449964A (en) * | 2014-10-28 | 2015-03-25 | 无锡乐华自动化科技有限公司 | Automotive antirust lubricating oil |
| JP6655284B2 (en) * | 2014-12-11 | 2020-02-26 | シェルルブリカンツジャパン株式会社 | Lubricating oil composition |
| CN104911001B (en) * | 2015-06-05 | 2018-04-24 | 广西大学 | Miller cycle engine lubricant compositions |
| CN107312593A (en) * | 2017-06-09 | 2017-11-03 | 中国石油化工股份有限公司 | Diesel engine oil compositions of CF 4 and application thereof |
| CN107338092A (en) * | 2017-06-09 | 2017-11-10 | 中国石油化工股份有限公司 | Diesel locomotive fluid composition and application thereof |
| CN109679728B (en) * | 2017-10-18 | 2022-06-24 | 中国石油化工股份有限公司 | Gasoline engine lubricating oil composition and preparation method thereof |
| CN114752425A (en) * | 2021-01-11 | 2022-07-15 | 中国石油天然气股份有限公司 | Additive composition |
| CN116064188B (en) * | 2021-11-04 | 2024-10-11 | 中国石油化工股份有限公司 | Lubricating oil composition and method for producing the same |
| CN116162485A (en) * | 2023-03-17 | 2023-05-26 | 中国石油化工股份有限公司 | Crude oil nucleophilic deconstructing auxiliary agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493671A (en) * | 2002-09-13 | 2004-05-05 | ŵ��ķ | Combination of low ash lubricating oil composition and low sulfur fuel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493671A (en) * | 2002-09-13 | 2004-05-05 | ŵ��ķ | Combination of low ash lubricating oil composition and low sulfur fuel |
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