CN1175622A - Ship IC engine oil composition - Google Patents
Ship IC engine oil composition Download PDFInfo
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- CN1175622A CN1175622A CN 96109561 CN96109561A CN1175622A CN 1175622 A CN1175622 A CN 1175622A CN 96109561 CN96109561 CN 96109561 CN 96109561 A CN96109561 A CN 96109561A CN 1175622 A CN1175622 A CN 1175622A
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Abstract
A lubricant composition with total base number greater than 70 mg KOH/g for the lubrication between cylinder sleeve and piston of low-speed crosshead diesel engine for ship contains boronated amine thiophosphate (NSPN), high-alkali sulfurized calcium alkylphenate, high-alkali calcium salicylate, dinonylphenol polyoxyethylene ether (DNP), polyisobutylene butanedioylimine, zinc dialkyldithiophosphate and low-viscosity index mineral oil.
Description
The present invention relates to a kind of ship IC engine oil composition, particularly a kind of lubricant compositions that can satisfy lubricating requirement between low speed cross hair style ship engine cylinder sleeve and the piston ring, it should possess good detergency and resistance to abrasion.Specifically, the present invention relates to except that containing conventional detergent-dispersant additive, antioxygen corrosion inhibitor, also contain a certain amount of polyoxyethylene phenoxyl compound (hereinafter to be referred as DNP), boronation thiophosphatephosphorothioate amine salt (hereinafter to be referred as NSPN).
As everyone knows, in marine low-speed cross diesel motor operational process, except that main corrosive wear, frictional wear is to a certain degree arranged still between piston ring and the cylinder sleeve.Therefore, remove the adding high alkaline metal detergent and neutralize, reduce outside the corrosive wear owing to using the acidic substance that high-sulfur fuel generates, also should suitably add some anti-wear agents, diffusant, reducing frictional wear, thereby prolong engine work-ing life, reduce maintenance cost.
United States Patent (USP) U.S.P 4,483,775 relates to a kind of lubricating oil composition, by adding the abrasion resistance of anti-wear agent raising oil product.The diisopropyl disulfide that comprised basicity calcium sulphonate, 3.5% (m) of this combination is for phosphoric acid succinimide salt, the di-isopropyl thiophosphoric acid zinc of 8.1mol/kg.
United States Patent (USP) U.S.P 4,842,755 relates to a kind of lubricant compositions, and composition contains boronation ashless dispersant (the rare reactant with the polyamides acid anhydride of the poly-isobutyl of boronation) 0.5% (m).Cross basicity metal detergent amount 12.1% (m) and zinc dialkyl dithiophosphate, 0.10% (m).The content of boron and zinc is respectively 0.01-0.016 and 0.02-0.023% (m) in the composition, and the base number of oil product is 60mgKOH/g.
United States Patent (USP) U.S.P 4,668,409 relates to a kind of lubricating oil composition, by adding the abrasion resistance of anti-wear agent raising oil product.In the composition that contained the basicity calcium sulphonate, add the alkyl pyrocatechol phosphorodithioate of 0.05-1.0% (m), abrasion resistance is improved.The structural formula of anti-wear agent is as follows:
R=C in the formula
10-18Alkyl, M are basic metal or transition metal, and n is the valency of M.
This 4,358,387 relates to a kind of lubricating oil composition United States Patent (USP) U.S., has added the anti-friction composition N-alkyl glycine derivative of 1.0% (m) in the composition, and the structural formula of anti-friction composition N-alkyl glycine derivative is:
As R '=R "=during hydroxyalkyl, compound is:
Work as R '=H, R "=CH
2CH
2NH
2The time, compound is:
R=C in the formula
16-18Alkyl.
United States Patent (USP) U.S.P 4,420,407 relates to a kind of lubricating oil composition, has added the anti-friction composition N-second hydroxyalkyl succinimide of 1.0% (m) in the composition, and the abrasion resistance of lubricant is improved.
The structural formula of N-second hydroxyalkyl succinimide is as follows:
R=C in the formula
12-18Alkyl, R=C
12The time the most effective.
United States Patent (USP) U.S.P 4,505,835 relates to a kind of lubricating oil composition, has added the reactant that 1.0% (m) has this acid anhydride of Malaysia and amine in the composition, evaluates with the SEFT test, and the resistance to abrasion of composition improves 13.1%.
United States Patent (USP) U.S.P 4,402,845 relates to a kind of adding diffusant and improves the lubricating oil composition performance, and the poly-ethoxy by adding 1% (m) in the composition that contains basicity calcium sulphonate and ashless dispersant is at glycol (R-CH
2O-(CH
2CH
2O)
20H, R=C
12-18Alkyl), make the diffustivity of oil product improve 94% (diffusion diameter).
United States Patent (USP) U.S.P4,479,882 relate to a kind of adding diffusant improves lubricating oil composition, by the rare phenoxyl compound of the polyoxy second that adds 2% (m) in the composition that contained basicity calcium sulphonate and ashless dispersant
, R=C
12-18Alkyl), can make the diffusion diameter of oil product increase by 123%.
United States Patent (USP) U.S.P4,414,123, U.S.P4,438,005 relate separately to a kind of adding diffusant polyethoxye sorbose acid esters and the rare ester of polyoxy second improves diffusible composition, and diffusion diameter has improved 89%, 167% respectively.
In the ship cylinder oil formula, with regard to metal detergent, have following several compound:
1. SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and sulfonate are compound
2. SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and high-alkali naphthenate are compound
3. high-alkali naphthenate and high-alkali salicylate are compound
Above formulation types is used widely in many oil companies.
In a word, in above-mentioned document and patent, do not have one piece openly to control SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and high-alkali salicylate compositely proportional, do not have public use boronation thiophosphatephosphorothioate amine salt to improve the patent of composition resistance to abrasion yet.
The object of the present invention is to provide a kind of lubricant compositions that can satisfy lubricating requirement between large-sized low-speed cross-head diesel engine piston and the cylinder sleeve.
The invention provides a kind of large-sized low-speed cross-head diesel engine that can suppress effectively owing to the effect corrosive wear that causes of high-sulfur fuel and frictional wear to a certain degree, and can improve the high temperature detergency of oil product.The following component that said composition is assisted composition as the lubricated graininess oil and the conduct of major ingredient:
A: base of a pillar thiophosphatephosphorothioate amine salt (NSPN)
B: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER
C: high-alkali calcium salicylate
D: binonylphenol polyoxydivinyl ether (DNP)
E: the poly-rare succimide of isobutyl
F: zinc dialkyl dithiophosphate
Wherein component A accounts for the 0.1-2.0% of lubricant compositions quality; Component B accounts for the 10.0-20.0% of lubricant compositions quality; Component C accounts for the 3.0-18.0% of lubricant compositions quality; Component D accounts for the 0.01-2.0% of lubricant compositions quality; Component E accounts for the 2.0-5.0% of lubricant compositions quality; Component F accounts for the 0.1-1.0% of lubricant compositions quality.
Basis of the present invention is that SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and high-alkali calcium salicylate have preferable compatibleness, composition has good detergency and resistance to abrasion, boronation thiophosphatephosphorothioate amine salt particularly, the resistance to abrasion of composition is improved, and other use propertieies are had no adverse effects.
The structure of employed NSPN is as follows among the present invention:
Wherein: the R representative has the alkyl of 1-12 carbon atom;
R ' representative has the alkyl of 6-20 carbon atom.
It is to be reacted under certain condition by phosphide, sulfide and boride to make, its sulphur, phosphorus, nitrogen, boron content are respectively: 5.0-6.5 (m) %, 5.0-6.5 (m) %, 2.5-3.5 (m) %, 1.5-1.9 (m) % has good extreme pressure anti-wear and thermal oxidation stability.DNP in the composition can make oil product diffusion rapidly on cylinder sleeve, cooperatively interacts with zinc dialkyl dithiophosphate, NSPN in the composition, makes oil product have excellent abrasion resistance.Thereby determine that it is the key component of said composition.
The structure of employed DNP is as follows among the present invention:
R=C in the formula
9-18Alkyl, n=12-20.
It is the product that is made by binonylphenol and polyether reactant, can reduce the surface tension of oil product, makes oil product be diffused into the cylinder sleeve surface rapidly, has guaranteed the oil film on cylinder sleeve surface.
Other additives belong to known content, need not give unnecessary details at this.
In the composition among the present invention, six kinds of components of various additives (referring to A, B, C, D, E, F)) ratio determines that by four ball friction-wear tests, detergency strenuous test, diffustivity test etc. the actual applying working condition of lubricating oil has been simulated in these tests effectively.
During composition among the present invention is applicable to, the mineral oil of low-viscosity index.In the sufficient oil product of preparation, the effective level of each component is as follows:
Form m% m%
General range preferable range boronation thiophosphatephosphorothioate amine salt, (NSPN) the high-alkali calcium salicylate 3.0-18.0 5.0-15.0 of 0.1-2.0 0.2-1.5 SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER 10.0-20.0 10.0-18.0 binonylphenol Soxylat A 25-7, (DNP) 0.01-2.0 0.05-2.0 polyisobutene succinimide 2.0-5.0 2.5-4.0 zinc dialkyl dithiophosphate 0.1-1.0 0.1-0.8 cycloalkyl or intermediate base base oil surplus surplus
Above-mentioned each component was fully stirred three hours down at 85 ± 5 ℃, can obtain the marine cylinder oil that base number is 70mgKOH/g.
Following example is to further specify of the present invention, is not to limit the scope of the invention.
Embodiment 1
The 70TBN marine cylinder oil that preparation one full component viscosity is the SAE50 level, it contains boronation thiophosphatephosphorothioate amine salt (NSPN), SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, high-alkali calcium salicylate, binonylphenol polyoxydivinyl ether (DNP), the poly-rare succimide of isobutyl, zinc dialkyl dithiophosphate.The data that obtain thus are summarized in table 1.
Table 1
| Comparative example | Embodiment | Test method | |||
| Component m% | Boronation thiophosphatephosphorothioate amine salt, (1) SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, (2) high-alkali calcium salicylate, (3) binonylphenol polyoxydivinyl ether, (4) the poly-rare succimide of isobutyl, (5) zinc dialkyl dithiophosphate, (6) | 0.0 16.0 10.0 0.01 3.5 0.2 | ??0.7 ??16.0 ??10.0 ??0.01 ??3.5 ??0.2 | ||
| Test-results | High Temperature Detergent Experiment (reinforcement), level (7) | 3.5 | ??3.5 | ??SH/T269 | |
| Four ball friction-wear tests (8) | ????P B??，N | 1176.0 | ??1440.6 | ??GB/T3142 | |
| ????P D??，N | 2450.0 | ??2450.0 | |||
| ????ZMZ，N | 457.7 | ??621.3 | |||
| The diffustivity test, diffusion area mm 2(9) | 531 | ??531 | With reference to the Oronite method | ||
Annotate: (1) is Lanzhou oil-refining chemical head factory product, and sulphur, phosphorus, nitrogen, boron content are respectively: 5.0-6.5 (m) %, 5.0.6.5 (m) %, 2.5 ,-3.5 (m) %, 1.5-1.9 (m) %
(2) be Lanzhou oil-refining chemical head factory product, calcium contents 9,51%, base number are 255mgKOH/g.
(3) be Lanzhou oil-refining chemical head factory product, calcium contents 10.52%, base number are 297mgKOH/g.
(4) be Lanzhou oil-refining chemical head factory product, molecular weight is 880, the polymerization degree 15.
(5) be Lanzhou oil-refining chemical head factory product, total nitrogen content 1.48%, base number are 21mgKOH/g.
(6) be Lanzhou oil-refining chemical head factory product, zinc content 9.09%, phosphorus content cup 7.40%.
Represent with level that (7) level is the smaller the better.
(8) result is with P
B, P
D, ZMZ represents, is worth greatly more, resistance to abrasion is good more.
(9) area is big more, and diffustivity is good more.
Embodiment 2
The 70TBN marine cylinder oil that preparation one full component viscosity is the SAE50 level, it contains boronation thiophosphatephosphorothioate amine salt (NSPN), SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, high-alkali calcium salicylate, binonylphenol Soxylat A 25-7 (DNP), the poly-rare succimide of isobutyl, zinc dialkyl dithiophosphate.The data that obtain thus are summarized in table 2.
Table 2
| Comparative example | Embodiment | Test method | |||
| Component m% | The high-alkali calcium salicylate binonylphenol of boronation thiophosphate amine salt SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER polyoxydivinyl ether gathers the rare succimide zinc dialkyl dithiophosphate of isobutyl | ?0.7 ?16.0 ?10.0 ?0.0 ?3.5 ?0.2 | ?0.7 ?16.0 ?10.0 ?0.01 ?3.5 ?0.2 | ||
| Test-results | High Temperature Detergent Experiment (reinforcement), level | ?3.5 | ?3.5 | ?SH/T269 | |
| Four ball friction-wear tests | ????P B，N | ?1176.0 | ?1440.6 | ?GB/T3142 | |
| ????P D，N | ?2450.0 | ?2450.0 | |||
| ????ZMZ，N | ?455.6 | ?621.3 | |||
| The diffustivity test, diffusion area mm 2 | ?491 | ?531 | With reference to the Oronite method | ||
Embodiment 3
The 70TBN marine cylinder oil that preparation one full component viscosity is the SAE50 level, it contains boronation thiophosphatephosphorothioate amine salt (NSPN), SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, high-alkali calcium salicylate, binonylphenol Soxylat A 25-7 (DNP), the poly-rare succimide of isobutyl, zinc dialkyl dithiophosphate.The data that obtain thus are summarized in table 3.
Table 3
| Comparative example | Embodiment | Test method | |||
| Component m% | The high-alkali calcium salicylate binonylphenol of boronation thiophosphate amine salt SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER polyoxydivinyl ether gathers the rare succimide zinc dialkyl dithiophosphate of isobutyl | 0.7 16.0 10.0 2.0 3.5 0.2 | 0.7 16.0 10.0 0.01 3.5 0.2 | ||
| Test-results | High Temperature Detergent Experiment (reinforcement), level | 3.5 | 3.5 | ??SH/T269 | |
| Four ball friction-wear tests | ????P B，N | 1234.8 | 1440.6 | ??GB/T3142 | |
| ????P D，N | 2450.0 | 2450.0 | |||
| ????ZMZ，N | 581.1 | 621.3 | |||
| Diffustivity test diffusion area mm 2 | 804 | 531 | With reference to the Oronite method | ||
Embodiment 4
The 70TBN marine cylinder oil that preparation one full component viscosity is the SAE50 level, it contains boronation thiophosphatephosphorothioate amine salt (NSPN), SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, high-alkali calcium salicylate, binonylphenol Soxylat A 25-7 (DNP), the poly-rare succimide of isobutyl, zinc dialkyl dithiophosphate.The data that obtain thus are summarized in table 4.
Table 4
| Comparative example | Embodiment | Test method | |||
| Component m% | The high-alkali calcium salicylate binonylphenol of boronation thiophosphate amine salt SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER polyoxydivinyl ether gathers the rare succimide zinc dialkyl dithiophosphate of isobutyl | 0.7 16.0 10.0 0.01 3.5 0.2 | 0.7 16.0 10.0 0.01 3.5 0.2 | ||
| Test-results | High Temperature Detergent Experiment (reinforcement), level | 3.5 | 3.5 | ??SH/T269 | |
| Four ball friction-wear tests (8) | ????P B，N | 1440.6 | 1440.6 | ??GB/T3142 | |
| ????P D，N | 2450.0 | 2450.0 | |||
| ????ZMZ，N | 528.0 | 621.3 | |||
| Diffustivity test diffusion area mm 2 | 531 | 531 | With reference to the Oronite method | ||
Embodiment 5
The 70TBN marine cylinder oil that preparation one full component viscosity is the SAE50 level, it contains boronation thiophosphatephosphorothioate amine salt (NSPN), SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, high-alkali calcium salicylate, binonylphenol Soxylat A 25-7 (DNP), the poly-rare succimide of isobutyl, zinc dialkyl dithiophosphate.The data that obtain thus are summarized in table 5.
Table 5
| Embodiment | Test method | |||
| Component m% | The high-alkali calcium salicylate binonylphenol of boronation thiophosphate amine salt SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER polyoxydivinyl ether gathers the rare succimide zinc dialkyl dithiophosphate of isobutyl | 0.2 16.0 10.0 0.01 3.5 0.7 | ||
| Test-results | High Temperature Detergent Experiment (reinforcement), level | 3.5 | ????SH/T269 | |
| Four ball friction-wear tests | ????P B，N | 1440.6 | ????GB/T3142 | |
| ????P D，N | 2450.0 | |||
| ????ZMZ，N | 621.3 | |||
| The diffustivity test, diffusion area mm 2 | 531 | With reference to the Oronite method | ||
| BOLNES-DNL bench testing (1) | By | |||
Annotate: (1) Bolnes-3DNL engine is the typical equipments of evaluation marine cylinder oil, comments
Decide the result and show, the detergency of embodiment 5 and reference oil Mobilgard-570,
The resistance to abrasion performance is suitable.
Claims (9)
1. lubricant compositions, comprise boronation thiophosphatephosphorothioate amine salt (A), SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (B), middle and high buck poplar acid calcium salt (C), binonylphenol Soxylat A 25-7 (D), polyisobutene succinimide (E), zinc dialkyl dithiophosphate (F) and in, the mineral oil basis oil of low-viscosity index.
2. according to the described composition of claim 1, it is characterized in that: its structure of 0.1-2.0% that component (A) accounts for the combination total mass is:
Wherein: the R representative has the alkyl of 1-12 carbon atom;
R ' representative has the alkyl of 6-20 carbon atom.
3. according to the described combination of claim 1, it is characterized in that: (B accounts for the 10.0-20.0% of composition total mass to component.
4. according to the described composition of claim 1, it is characterized in that: component (C) accounts for the 3.0-18.0% of composition quality.
5. according to the described composition of claim 1, it is characterized in that: component (D) accounts for the 0.01-2.0% of composition total mass, and its structure is:
The R representative has the alkyl of 9-18 carbon atom, and the span of n is 12-20.
6. according to the described composition of claim 1, it is characterized in that: component (E) accounts for the .0-5.0% of composition total mass.
7. according to the described composition of claim 1, it is characterized in that: component (F) accounts for the 0.1-1.0% of composition total mass.
8. according to the described composition of claim 1, its total basicnumber is greater than 70mgKOH/g.
9. according to the described composition of claim 1, can be used for using lubricated between the marine low-speed cross-head diesel engine cylinder sleeve of high-sulfur alkene material and the piston.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109561A CN1053465C (en) | 1996-08-30 | 1996-08-30 | Ship IC engine oil composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109561A CN1053465C (en) | 1996-08-30 | 1996-08-30 | Ship IC engine oil composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175622A true CN1175622A (en) | 1998-03-11 |
| CN1053465C CN1053465C (en) | 2000-06-14 |
Family
ID=5120441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109561A Expired - Lifetime CN1053465C (en) | 1996-08-30 | 1996-08-30 | Ship IC engine oil composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053465C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100513539C (en) * | 2003-02-20 | 2009-07-15 | 中国石油天然气股份有限公司 | Low ash lubricating oil composition for gas engine |
| CN102690713A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for ship outboard engine |
| CN105238524A (en) * | 2015-10-19 | 2016-01-13 | 中国石油化工股份有限公司 | Diesel engine oil composition and application |
| CN107502411A (en) * | 2017-09-20 | 2017-12-22 | 温岭市朗熙石油化学科技有限公司 | A kind of ship universal diesel engine oil |
| CN110317661A (en) * | 2018-03-28 | 2019-10-11 | 中国石油化工股份有限公司 | Ship use intermediate speed tubular piston-mode motor lubricant oil composite and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966722A (en) * | 1988-11-16 | 1990-10-30 | Exxon Chemical Patents Inc. | Oil additive compositions exhibiting reduced haze containing polymeric viscosity index improver |
| US5120566A (en) * | 1989-11-10 | 1992-06-09 | Fuji Oil Company, Limited | Process for producing water-containing chocolate |
| CN1020044C (en) * | 1990-06-20 | 1993-03-10 | 中国石油化工总公司石油化工科学研究院 | EP oil composition for industrial gears |
| CN1062755A (en) * | 1990-12-29 | 1992-07-15 | 张俊堂 | Metal cold molding treating lubricating agent and preparation method thereof |
-
1996
- 1996-08-30 CN CN96109561A patent/CN1053465C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100513539C (en) * | 2003-02-20 | 2009-07-15 | 中国石油天然气股份有限公司 | Low ash lubricating oil composition for gas engine |
| CN102690713A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for ship outboard engine |
| CN102690713B (en) * | 2011-03-24 | 2013-12-25 | 中国石油化工股份有限公司 | Lubricant composition for ship outboard engine |
| CN105238524A (en) * | 2015-10-19 | 2016-01-13 | 中国石油化工股份有限公司 | Diesel engine oil composition and application |
| CN105238524B (en) * | 2015-10-19 | 2018-04-13 | 中国石油化工股份有限公司 | Diesel engine oil composition and purposes |
| CN107502411A (en) * | 2017-09-20 | 2017-12-22 | 温岭市朗熙石油化学科技有限公司 | A kind of ship universal diesel engine oil |
| CN107502411B (en) * | 2017-09-20 | 2020-04-07 | 浙江朗熙石油化学科技有限公司 | Universal diesel engine oil for ships |
| CN110317661A (en) * | 2018-03-28 | 2019-10-11 | 中国石油化工股份有限公司 | Ship use intermediate speed tubular piston-mode motor lubricant oil composite and preparation method thereof |
| CN110317661B (en) * | 2018-03-28 | 2022-07-15 | 中国石油化工股份有限公司 | Lubricating oil composition for marine medium-speed trunk piston engine and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1053465C (en) | 2000-06-14 |
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Addressee: Lanzhou Oil Refining Chemical Genernal Plant, Chinese Petro-Chemical Corp. Document name: Notification of Expiration of Patent Right Duration |