CN101497842A - Low-deposition fuel consumption-saving type engine oil composition - Google Patents
Low-deposition fuel consumption-saving type engine oil composition Download PDFInfo
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Abstract
The invention provides a low deposition consumable engine oil composition saving fuel having excellent deposit resistance under high temperature more than 400 degrees centigrade and observably reducing the friction coefficient between metals. The low deposition consumable engine oil composition saving fuel is characterized that: the dynamic viscosity under 100 degrees centigrade is more than 4.5 mm2/s, and mineral oil with viscosity index more than 120 and/or amine antioxidant containing more than 1.5 mass % in total of synthetic oil and/or phenol antioxidant, and further containing more than 0.02 mass % of organic molybdenum compound measuring by molybdenum (Mo).
Description
Technical field
The present invention relates to good, and make the significantly reduced low-deposition fuel consumption-saving type engine oil of intermetallic frictional coefficient above the anti-deposition under 400 ℃ the high temperature.
Background technology
In recent years, for preventing Greenhouse effect, reduce specific fuel consumption, the inhibition CO of automobile
2Discharging just becoming necessary problem.Reduce the specific fuel consumption of automobile, the high efficiency of engine has importantly adopted variable valve mechanism, lean-burnization, straight sprayization, the technology such as installation of turbo-supercharger in addition in the petrol engine.On the other hand, also can make contributions, therefore want in sliding component, to use low-friction material and adopt fuel consumption-saving type engine oil reducing specific fuel consumption (energy-conservation) owing to reduce the friction of engine.
During known manufacturing fuel consumption-saving type engine oil, effectively mixing molybdenum dithiocarbamate organic-molybdenums such as (MoDTC) is that friction improver (Friction Modifier is also referred to as FM below) is as the additive that reduces friction.Yet organic-molybdenum is surpassing of producing when being reported in the air cooling turbine engine by hot dipping (heat soak) of FM can make deposition increase (non-patent literature 1) in 400 ℃ the high-temperature area.
Can envision, for reducing the specific fuel consumption of automobile, the miniaturization of being undertaken by the installation turbo-supercharger (reducing free air delivery when keeping engine output) from now on will constantly improve, and needs to improve the anti-deposition of engine oil.That is, fuel consumption-saving type engine oil is from now on compared with engine oil in the past, and anti-deposition aspect that must be at high temperature is better.
On the other hand, organic molybdenum is by forming MoS in the metallic surface
2Tunicle is compared with situation of not adding FM or Ashless type FM and can significantly be reduced frictional coefficient.Therefore, even under the situation of having mixed organic molybdenum, it also is important problem that the sedimentary engine oil that reduces under the high temperature is provided.
Non-patent literature 1:S.Yoshida ﹠amp; Y.Naitoh contains the evaluation (Evaluation of Low Phosphorous Engine Oil Containing MoDTC) of the low-phosphorous engine oil of MoDTC, SAE technical article (SAE Technical Paper) 2007-01-1962 (2007)
Summary of the invention
In view of the foregoing, problem of the present invention provide surpass anti-deposition under 400 ℃ the high temperature good, also intermetallic frictional coefficient can be maintained significantly lower level, reduce the low-deposition fuel consumption-saving type engine oil of specific fuel consumption.
The present inventor has carried out conscientiously research for solving above-mentioned problem, found that to the mineral oil with specific dynamic viscosity and viscosity index and/or synthetic be mix in the base oil a certain amount of above ashless be antioxidant and organic molybdenum and the composition conduct at high temperature to have a fuel consumption-saving type engine oil of good anti-deposition useful.The present invention is based on the invention of this discovery.
That is, the present invention is a kind of low-deposition fuel consumption-saving type engine oil composition, and said composition is characterised in that the dynamic viscosity that contains under 100 ℃ is 4.5mm
2Above and the viscosity index of/s is mineral oil and/or the synthetic oil 120 or more, and summation is that the above amine of 1.5 quality % is that antioxidant and/or phenol are antioxidant, and counts organic molybdenum more than the 0.02 quality % with molybdenum (Mo).The preferred molybdenum dithiocarbamate of described organic molybdenum (MoDTC).
Low-deposition fuel consumption-saving type engine oil composition of the present invention has aforesaid formation, and is therefore good in the anti-deposition that surpasses under 400 ℃ the high temperature, also plays to make the significantly reduced special-effect of intermetallic frictional coefficient.Therefore, applicable to oil engine, the petrol engine of turbo-supercharger is installed particularly.That is, can bring into play and reduce the sedimental generation in the turbo-supercharger and the intermetallic frictional coefficient of engine sliding part is significantly reduced, reduce the special-effect of specific fuel consumption by this.
Embodiment
In the engine oil composition of the present invention,,, can use in mineral oil, synthetic oil and their mixing oil any as long as viscosity index is more than 120 as lubricant base.Viscosity index is that generation oil that the high-viscosity index lubricating oil base oil more than 120 can get by the hydrocracking to the hydroisomerization that utilizes wax or mink cell focus carries out solvent dewaxing or Hydrodewaxing gets.Below an example of these method for makings is set forth more specifically.
The hydroisomerization of wax can carry out by the following method: with boiling point in 300～600 ℃ scope, the wax of carbon number in 20～70 scopes, for example by being that the slack wax that obtains of the solvent dewaxing operation of lubricating oil or the wax that obtained by the expense-holder synthetic (Fischer-Tropschsynthesis) of synthetic liquid fuels such as appropriate hydrocarbon gas etc. are raw material by mineral oil, at hydrogen partial pressure be 5～14MPa hydrogen in the presence of, be that 300～450 ℃, LHSV (liquid space velocity) are 0.1～2hr in temperature
-1Condition under make itself and hydroisomerisation catalysts, for example on aluminum oxide or silicon oxide-alumina supporter, carry in the 6A family metals such as 8 family's metals such as nickel, cobalt and molybdenum, tungsten more than one and catalyzer, zeolite catalyst or containing carrying platinum on the carrier of zeolite etc. and the catalyzer contact.At this moment, be preferably make straight catenate paraffin transformation efficiency more than 80%, make transformation efficiency to light ends below 40%.
On the other hand, the lubricant base of the used high viscosity index (HVI) of the present invention can obtain by the hydrocracking through mink cell focus as described below.The hydrocracking of mink cell focus can carry out by the following method: at hydrogen partial pressure be 7～14MPa hydrogen in the presence of, be that 350～450 ℃, LHSV (liquid space velocity) are 0.1～2hr in temperature
-1Condition under in making normal pressure distilled oil, vacuum distillate or the bright stock (brightstock) of boiling point in 300～600 ℃ scope that carried out hydrogenating desulfurization and denitrogenation as required and for example on silicon oxide-alumina supporter, carrying 8 family's metals such as nickel, cobalt more than a kind and in the 6A family metals such as molybdenum, tungsten more than a kind and catalyzer contact; Being preferably and making cleavage rate (quality of the minimizing of the cut more than 360 ℃ in resultant shared quality %) is 40～90%.
Though can generate oil or hydrocracking from the hydroisomerization that obtains by aforesaid method generates the oil fractionation and removes light ends and obtain lubricating oil distillate, if but this cut is not treated, then in general yield point and viscosity height, and viscosity index is not high enough, therefore can carry out dewaxing treatment, remove the dewax composition, obtain the %C that obtains in n-d-M ring analysis
PBe more than 80, yield point for below-10 ℃, viscosity index is the lubricant base more than 120.
Undertaken under the situation of removing of this wax composition by the solvent dewaxing processing, when above-mentioned light ends is removed in fractionation with the precise distillation device carry out fractionation by distillation, in advance cut, make the boiling point that obtains by the gas-chromatography distillation method being that method more than the 70 quality % can be carried out solvent dewaxing more efficiently and handled more than 371 ℃ but less than the ratio of 491 ℃ cut, therefore preferable.This solvent dewaxing processing for example can be used, and methyl ethyl ketone/toluene (volume ratio 1/1), carries out under-15～40 ℃ temperature under the condition in the scope of solvent/oil ratio 2/1～4/1 as dewaxing solvent.
On the other hand, undertaken by the Hydrodewaxing method under the situation of removing of wax composition, with the fractionation of light ends remove the degree that can impact Hydrodewaxing of proceeding to not, carry out with the precise distillation device behind the Hydrodewaxing fractionation by distillation, in advance cut, to make the boiling point that obtains by the gas-chromatography distillation method be that method efficient more than the 70 quality % is higher, therefore preferable more than 371 ℃ but less than the ratio of 491 ℃ cut.This Hydrodewaxing can by at hydrogen partial pressure be 3～15MPa hydrogen in the presence of, be that 320～430 ℃, LHSV (liquid space velocity) are 0.2～4hr in temperature
-1Condition under lubricating oil distillate is contacted with zeolite catalyst carry out, the yield point that makes final lubricant base is for below-10 ℃.
Can obtain viscosity index by aforesaid method is lubricant base more than 120, but also can further carry out solvent treatment or hydrofinishing as required.
In addition, as synthetic oil, can exemplify the oligopolymer of α-alkene, by di-carboxylic acid and monohydroxy-alcohol synthetic diester such as hexanodioic acids, by polyvalent alcohol and monocarboxylic acid synthetic polyol ester and their mixtures etc. such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethanes.
In addition, the mixing oil that suitable mineral oil and synthetic oil are combined also can be used as the base oil of this engine oil.
The organic molybdenum that uses in the engine oil of the present invention can exemplify molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), molybdenum amine complex etc., special preferred MoDTC.
MoDTC represents with following general formula (1).
In the formula, R represents to have the straight chain of 4～18 carbon and/or the alkyl and/or the alkenyl of side chain, and X represents Sauerstoffatom or sulphur atom, and the ratio of this Sauerstoffatom and sulphur atom is 1/3～3/1.The R preferred alkyl specifically can exemplify butyl, 2-ethylhexyl, isotridecyl, stearyl etc.4 R that are present in 1 molecule can be the same or different.In addition, also the R more than 2 kinds can be mixed use by different MoDTC.
As the antioxidant that uses in the engine oil of the present invention, can use phenol be antioxidant and amine be in the antioxidant at least any, be preferably and use both simultaneously.
As the preferred phenol that uses in the engine oil of the present invention is antioxidant, for example can exemplify the compound with following general formula (2) and (3) expression.
In the formula (2), the preferred carbon number of R is the alkyl below 20 more than 3, as the preferred alkyl of spy, can exemplify octyl group, stearyl.
As the preferred amine that uses in the engine oil of the present invention is antioxidant, for example can exemplify the compound with following general formula (4) and (5) expression.
The compound of formula (4) generally be make the reaction of N-phenylaniline and alkene and compound.In the formula (4), R is an alkyl, 5 positions is respectively arranged on each phenyl ring, add up to 10 positions and can replace, and the compound that replaces has taken place in the position that preferably has more than at least 1.The carbon number of alkyl is preferred more than 3 below 20, and R has under a plurality of situations, can be identical alkyl or different alkyl.Preferred alkyl can exemplify the alkyl of the straight or branched from the butyl to the nonyl.
In the formula (5), R is that carbon number is the alkyl below 20 more than 3, though in the formula (5) record be naphthyl and phenyl both the compound that replaces has all taken place, but also can be to have the position more than 1 that the compound that replaces has taken place on any group at least wherein, also can be respectively to have the position more than 1 that the compound that replaces has taken place on two groups.R has under a plurality of situations, and each R can be the same or different.In addition, special good be that R has 1 position that the compound that replaces has taken place on the octyl group of straight or branched or in nonyl, naphthyl or the phenyl any.
Phenol is that antioxidant and amine are that the summation of the content of antioxidant is more than the 1.5 quality %, and being preferably that proportioning becomes to make amine is that the nitrogen component (N) of antioxidant and the mass ratio (N/O) of the oxygen composition (O) that phenol is antioxidant are 0.20～0.35.If the summation of the content of described antioxidant less than 1.5 quality %, then can't obtain as the anti-deposition under the high temperature of target, for example the sediment yield of TEOST33C test is the following such performance of 45mg.In addition, be 0.20～0.35 if amine is the ratio of the quality of the quality of nitrogen component of antioxidant and the oxygen composition that phenol is antioxidant, then also have low friction such special-effect of life-span that can prolong MoDTC.
Can add sulfonate, phenates, salicylate etc. the washing agent of alkyl zinc dithiophosphate (ZnDTP), Ca, Mg, metals such as Ba, Na in the engine oil of the present invention as required, alkenyl succinimide etc. are ashless to be dispersion agent, and additives such as viscosity index improver, yield point depressant, metal passivator, rust-preventive agent and defoamer.
Embodiment
Below, by embodiment the present invention is specifically described.
It is base oil 1 (dynamic viscosity: 19.7mm that the generation oil that use gets the hydrocracking by mink cell focus carries out the mineral oil that Hydrodewaxing obtains
2/ s (40 ℃), 4.26mm
2/ s (100 ℃), viscosity index 124) and mineral oil be base oil 2 (dynamic viscosity: 35.3mm
2/ s (40 ℃), 6.36mm
2/ s (100 ℃), viscosity index 132) as base oil.
In the ratio shown in the table 1 in above-mentioned base oil, mix following phenol be antioxidant A, amine be antioxidant B, MoDTC, viscosity index improver and other additive as additive, be modulated into the engine oil of embodiment 1～5 and comparative example 1,2.In addition, the amine of interpolation be the nitrogen component (N) and the oxygen composition (O) that phenol is antioxidant of antioxidant ratio (quality: N/O) and Mo content be shown in table 1 in the lump.In addition, other additive is the additive agent mixture that is made of alkyl zinc dithiophosphate (ZnDTP), calcium sulphonate, alkenyl succinic imide, yield point depressant and defoamer, and embodiment and comparative example all add with identical addition.In embodiment 1～4 and comparative example 2, add viscosity index improver, making the dynamic viscosity of composition under 100 ℃ is 9.6～9.9mm
2/ s (be equivalent to SAE engine oil viscosity classification 30) in embodiment 5 and comparative example 1, adds viscosity index improver, and making the dynamic viscosity of composition under 100 ℃ is 8.6mm
2/ s (be equivalent to SAE engine oil viscosity classification 20).
Using with general formula (2) expression, substituent R is that antioxidant (oxygen level is 12.3 quality %) is antioxidant A as phenol as the phenol of octyl group.Use is as N-phenylaniline and 2,4, and the amine of the resultant of reaction of 4-2,4,4-Trimethyl-1-pentene is that antioxidant (nitrogen content is 4.5 quality %) is antioxidant B as amine.
Use is that the ratio of mixture, Sauerstoffatom and the sulphur atom of 2 ethylhexyls and isotridecyl is that 1/1 compound is as MoDTC with general formula (1) expression, R.
In addition, using polymethacrylate is that viscosity index improver is as viscosity index improver.
[table 1]
The embodiment of his-and-hers watches 1 and the engine oil of comparative example are implemented the TEOST33C test of ASTM D6334 defined respectively, estimate the anti-deposition properties under the high temperature.It the results are shown in table 2.
And the spreadsheet engine oil content that supplies of his-and-hers watches 1 is not implemented the SRV rub(bing)test under the following conditions, obtains the frictional coefficient of engine oil.It the results are shown in the hypomere of table 2.
SRV rub(bing)test condition
Contact conditions: column contacts (cylinder on block) with blocks
The test film material: column and blocks are AISI-52100
Sliding condition: load 400N, vibrational frequency 50Hz, amplitude 1.5mm, 100 ℃ of temperature
[table 2]
Can know clearly that from above result making the dynamic viscosity under 100 ℃ shown in the embodiment is 4.5mm
2Above and the viscosity index of/s is that to contain summation in mineral oil 120 or more and/or the synthetic oil be that the above amine of 1.5 quality % is that antioxidant and phenol are antioxidant, also contain that to count the sediment yield that the TEOST33C of the engine oil composition that the above organic molybdenum of 0.02 quality % forms tests with molybdenum (Mo) less, below 40mg, has good high temperature resistant deposition properties.Also as can be known, the intermetallic frictional coefficient of estimating with the SRV rub(bing)test of this engine oil composition is significantly lower, is below 0.06, and fuel consumption-saving is also good.
On the other hand, the dynamic viscosity of base oil under 100 ℃ is 4.26mm
2Though the engine oil composition intermetallic frictional coefficient of the comparative example 1 of/s is lower, the sediment yield of TEOST33C test reaches 74mg, and high temperature resistant deposition is poor.In addition as can be known, do not mix as the intermetallic frictional coefficient of the comparative example 2 of the MoDTC of FM highlyer more than 2 times than embodiment 1, fuel consumption-saving is poor.
Claims (2)
1. a low-deposition fuel consumption-saving type engine oil composition is characterized in that, the dynamic viscosity that contains under 100 ℃ is 4.5mm
2Above and the viscosity index of/s is mineral oil and/or the synthetic oil 120 or more, and summation is that the above amine of 1.5 quality % is that antioxidant and/or phenol are antioxidant, and counts organic molybdenum more than the 0.02 quality % with molybdenum (Mo).
2. low-deposition fuel consumption-saving type engine oil composition as claimed in claim 1 is characterized in that, organic molybdenum is molybdenum dithiocarbamate (MoDTC).
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| JP2008020090A JP5362228B2 (en) | 2008-01-31 | 2008-01-31 | Low deposit fuel-saving engine oil composition |
| JP2008020090 | 2008-01-31 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666661A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Petroleum-engine oil composition and application thereof |
| CN105524689A (en) * | 2014-10-21 | 2016-04-27 | 中国石油化工股份有限公司 | Low-viscosity high-efficiency energy-efficient engine oil and preparation technology thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6296503B2 (en) * | 2014-09-05 | 2018-03-20 | 株式会社Adeka | Method for increasing self-ignition point of engine oil of direct injection engine with supercharger, and self-ignition point increasing agent for engine oil of the same engine |
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| CN1247219A (en) * | 1998-09-09 | 2000-03-15 | 日石三菱株式会社 | Four-stroke engine oil compsns. for two-wheeled motorcycle |
| WO2007105769A1 (en) * | 2006-03-15 | 2007-09-20 | Nippon Oil Corporation | Lube base oil, lubricating oil composition for internal combustion engine, and lubricating oil composition for drive transmission device |
| WO2007114132A1 (en) * | 2006-03-31 | 2007-10-11 | Nippon Oil Corporation | Lube base oil, process for production thereof, and lubricating oil composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4778154B2 (en) * | 2001-03-15 | 2011-09-21 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
| JP4749613B2 (en) * | 2001-07-12 | 2011-08-17 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
| JP3933450B2 (en) * | 2001-11-22 | 2007-06-20 | 新日本石油株式会社 | Lubricating oil composition for internal combustion engines |
| JP4327519B2 (en) * | 2002-06-28 | 2009-09-09 | 新日本石油株式会社 | Lubricating oil composition |
| PL1878784T3 (en) * | 2005-04-20 | 2013-07-31 | Jx Nippon Oil & Energy Corp | Long-life fuel-saving engine oil composition |
| JP5137314B2 (en) * | 2006-03-31 | 2013-02-06 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating base oil |
| JP4945179B2 (en) * | 2006-07-06 | 2012-06-06 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
-
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- 2008-01-31 JP JP2008020090A patent/JP5362228B2/en active Active
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- 2009-01-19 CN CNA2009100028383A patent/CN101497842A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247219A (en) * | 1998-09-09 | 2000-03-15 | 日石三菱株式会社 | Four-stroke engine oil compsns. for two-wheeled motorcycle |
| WO2007105769A1 (en) * | 2006-03-15 | 2007-09-20 | Nippon Oil Corporation | Lube base oil, lubricating oil composition for internal combustion engine, and lubricating oil composition for drive transmission device |
| WO2007114132A1 (en) * | 2006-03-31 | 2007-10-11 | Nippon Oil Corporation | Lube base oil, process for production thereof, and lubricating oil composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666661A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Petroleum-engine oil composition and application thereof |
| CN105524689A (en) * | 2014-10-21 | 2016-04-27 | 中国石油化工股份有限公司 | Low-viscosity high-efficiency energy-efficient engine oil and preparation technology thereof |
| CN105524689B (en) * | 2014-10-21 | 2019-05-10 | 中国石油化工股份有限公司 | A kind of low-viscosity high-efficiency and energy-saving type engine oil and its preparation process |
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| JP5362228B2 (en) | 2013-12-11 |
| JP2009179718A (en) | 2009-08-13 |
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