WO2005026301A1 - Long life lubricating oil composition using particular antioxidant components - Google Patents
Long life lubricating oil composition using particular antioxidant components Download PDFInfo
- Publication number
- WO2005026301A1 WO2005026301A1 PCT/US2004/027184 US2004027184W WO2005026301A1 WO 2005026301 A1 WO2005026301 A1 WO 2005026301A1 US 2004027184 W US2004027184 W US 2004027184W WO 2005026301 A1 WO2005026301 A1 WO 2005026301A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- volume
- oil
- ashless
- alkylthiocarbamoyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/027—Neutral salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to gas engine oils. More particularly the present invention relates to gas engine oils that provide enhanced resistance to oxidation, nitration and viscosity increase.
- Typical natural gas fired engines such as those used in the petroleum industry to compress natural gas at well heads and along pipelines have up to 16 cylinders, often generating between 500 to 3000 HP. These engines normally are run continuously near full load conditions with shut downs being primarily for maintenance such as for oil changes. Such continuous operation near full load, of course, places severe demands on the engine lubricant. Indeed, because the lubricant is subjected to a high temperature environment, oxidation processes can occur rapidly which limit lubricant life. Also, natural gas engines emit nitrogen oxides (NO x ), some of which come into contact with the lubricant resulting in nitration processes also limiting lubricant life. Typically these processes are accompanied by increases in oil viscosity.
- NO x nitrogen oxides
- base oils are formulated with various additives such as dispersants, detergents, antioxidants, viscosity index improvers and the like to provide a lubricating oil composition.
- additives such as dispersants, detergents, antioxidants, viscosity index improvers and the like to provide a lubricating oil composition.
- This art of lubricating oil formulation has become increasingly more complex with ever more stringent requirements by end-users. Indeed, experience has shown that incorporation of one type of additive in a lubricant composition can have a negative impact on the function of another type of additive. Consequently, extensive research continues in the quest for lubricants of improved life and function.
- An object of the present invention is to provide a gas engine lubricating composition that has enhanced resistance to oxidation and nitration.
- Another object of the invention is to provide a gas engine lubricating composition that has improved life as evidenced by reduction in viscosity increase.
- a natural gas engine lubricant composition having enhanced resistance to oxidation, nitration and viscosity increase comprises:
- a minor amount of a detergent mixture comprising low/neutral TBN and over based metallic detergents, selected from the group consisting of alkali and alkaline earth sulphonates, phenates, and salicylates;
- a zinc dihydrocarbyl dithiophosphate in an amount sufficient to provide the lubricant composition with from 250 to 450 wppm of phosphorus.
- gas engine oil additives also may be present. These include: ashless dispersants, metal passivators, pour point depressants, VI improvers and antifoamants.
- the lubricating oil composition of the invention comprises a major amount of a lubricating oil basestock which may be a mineral oil, synthetic oil or blends of oils to give a basestock of the desired viscosity for a natural gas engine oil.
- a lubricating oil basestock which may be a mineral oil, synthetic oil or blends of oils to give a basestock of the desired viscosity for a natural gas engine oil.
- the basestock of the invention will have a kinematic viscosity at 100°C in the range of about 5 to about 16 cSt and preferably from about 10 to about 13 cSt.
- API category Group II basestocks are especially preferred.
- the composition of the invention includes a mixture of low/neutral TBN and overbased (high TBN) metallic detergents selected from the groups consisting of alkali and alkaline earth metal sulphonates, phenates, and salicylates.
- the metallic detergents will be calcium sulphonates, calcium phenates and calcium salicylates.
- Low/neutral TBN metallic detergents typically have a TBN in the range of about 10 to about 80.
- High TBN metallic detergents typically have a TBN in the range of about 150 to 300 or higher.
- the metallic detergents are used in amounts sufficient to contribute a sulfated. ash (ASTM D-874) to the formulated lubricant oil composition of about 0.2 mass % to about 2.0 mass %.
- the metallic detergents comprise from about 0.5 volume % to about 10 volume % and preferably 0.5 volume % to 5.0 volume % of the lubricating composition.
- the volume ratio (based on active ingredient) of overbased to low/neutral TBN metallic detergents is in the range of from about 0.05 to 3.5, and preferably about 0.25 to 1.0.
- Suitable alkylthiocarbamoyl compounds are represented by the formula:
- R 1 , R 2 , R 3 and R 4 are the same or different linear and branched alkyl groups of from 1 to 18 carbon atoms
- X is S, S-S, S-(CH 2 ) y -S, S-CH 2 -CH(R 5 )-S
- y is an integer of " 1 to 4
- R 5 is an alkyl group of 1 to 2 carbons.
- R 1 , R 2 , R 3 and R 4 are C 4 alkyl groups
- X is S(CH 2 ) y S
- Y is 1-3.
- the alkylthiocarbamoyl compound when used in the absence of the ashless, non-sulfur containing, hindered phenol generally comprises from about 0.25 volume % to about 2.0 volume % and preferably 0.5 volume % to 1.5 volume % of the total volume of the lubricating oil composition.
- the composition of the invention contains an antioxidant comprising a mixture of an alkylthiocarbamoyl compound and an ashless, sulfur free, hindered phenol.
- suitable alkylthiocarbamoyl compounds are represented by the same formula above.
- the hindered phenols suitable for use in conjunction with the alkylthiocarbamoyl compounds may be represented by the following formulae: and
- R l5 R 2 and R 3 are the same or different alkyl groups of 1 to 18 carbon atoms.
- the antioxidant is a mixture of alkylthiocarbamoyl and ashless, non-sulfur containing hindered phenols
- the alkyl dithiocarbamoyl comprises 0.25 volume % to 1.5 volume %, and preferably 0.5 volume % to 1.0 volume % of the composition and the phenol from 0.25 volume % to 1.5 volume % and preferably 0.5 volume% to 1.0 volume %.
- the natural gas engine lubricating composition also includes a zinc dihydrocarbyl dithiophosphate (ZDDP) or mixture of ZDDPs in which the hydrocarbyl groups may be the same or different alkyl groups or alkylaryl groups with the alkyl group, in each instance, having 3 to about 18 carbon atoms.
- the hydrocarbyl group is an alkyl group.
- the ZDDP or ZDDP mixture is present in the amount sufficient to provide the lubricating oil composition with 250 to 450 wppm of phosphorus.
- the invention also contemplates the use of other gas engine oil additives such as ashless dispersants, metal passivators, pour point depressants, VI improvers and antifoamants. Some of these additives are only required in minor amounts (antifoamants, metal passivators), while others may be required in significant amounts (dispersants). Thus, these additives will typically range from 0.01 volume % to about 10 volume % based on the total volume of the engine oil composition.
- Table 1 below details a series of formulations: (a) two for particularly preferred embodiments of the invention and (b) three other formulations included for comparative purposes.
- the basestock in all formulations was an API Group II category basestock. All oils were SAE 40 grades with nominally 0.45 mass % sulphated ash.
- Comparative Oil 1 is a low ash commercial gas engine oil which employed a commercial gas engine oil additive package.
- Reference Oil 1 was blended to represent an oil of U.S. Patent 6,140,282 while Comparative Oil 2 was blended to represent an oil of U.S. Patent 5,569,405.
- the various formulations were subjected to a nitration screener test and the results are presented in Table 1.
- the nitration screener test is a lab test which assesses several facets of the degradation of natural gas engine oils. All results are expressed as normalised against the results for the Reference Oil. Therefore, all results for the Reference Oil will have a result of 1.00 and any results lower than 1.00 signify enhanced performance.
- Comparative Oil 1 is inferior in all respects to the Reference Oil while Comparative Oil 2 provides better nitration and thickening control than the Reference Oil but inferior oxidation control.
- the Example 1 oil in contrast provides roughly equivalent oxidation control to that of the Reference Oil and improved nitration and thickening control.
- the oil of Example 2 is better than the Reference Oil in all three parameters.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04781798A EP1668101A1 (en) | 2003-09-05 | 2004-08-19 | Long life lubricating oil composition using particular antioxidant components |
CA002537266A CA2537266A1 (en) | 2003-09-05 | 2004-08-19 | Long life lubricating oil composition using particular antioxidant components |
BRPI0413688-8A BRPI0413688A (en) | 2003-09-05 | 2004-08-19 | natural gas engine lubricating oil composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50037803P | 2003-09-05 | 2003-09-05 | |
US60/500,378 | 2003-09-05 | ||
US10/861,601 US20050054543A1 (en) | 2003-09-05 | 2004-06-03 | Long life lubricating oil composition using particular antioxidant components |
US10/861,601 | 2004-06-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005026301A1 true WO2005026301A1 (en) | 2005-03-24 |
Family
ID=34228686
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/027184 WO2005026301A1 (en) | 2003-09-05 | 2004-08-19 | Long life lubricating oil composition using particular antioxidant components |
Country Status (5)
Country | Link |
---|---|
US (1) | US20050054543A1 (en) |
EP (1) | EP1668101A1 (en) |
BR (1) | BRPI0413688A (en) |
CA (1) | CA2537266A1 (en) |
WO (1) | WO2005026301A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7309681B2 (en) * | 2003-05-02 | 2007-12-18 | Exxonmobil Research And Engineering Company | Ashless lubricating oil composition with long life |
US8754017B2 (en) * | 2008-07-16 | 2014-06-17 | The Lubrizol Corporation | Lubricant for natural gas engines |
US8841243B2 (en) | 2010-03-31 | 2014-09-23 | Chevron Oronite Company Llc | Natural gas engine lubricating oil compositions |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0528610A1 (en) * | 1991-08-09 | 1993-02-24 | Oronite Japan Limited | Low phosphorous engine oil composition and additive compositions |
EP0588561A1 (en) * | 1992-09-14 | 1994-03-23 | Oronite Japan Limited | Low phosphorous engine oil compositions and additive compositions |
US5672572A (en) * | 1993-05-27 | 1997-09-30 | Arai; Katsuya | Lubricating oil composition |
EP0860495A2 (en) * | 1997-02-03 | 1998-08-26 | Tonen Corporation | Lubricating oil composition |
EP1104800A2 (en) * | 1999-12-02 | 2001-06-06 | Oronite Japan Limited | Lubricating oil composition for gas engines |
EP1418220A2 (en) * | 2002-10-31 | 2004-05-12 | Chevron Oronite Company LLC | A low-phosphorus lubricating oil composition for extended drain intervals |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5911397A (en) * | 1982-06-09 | 1984-01-20 | Idemitsu Kosan Co Ltd | Fatigue life modifying lubricant |
US6140282A (en) * | 1999-12-15 | 2000-10-31 | Exxonmobil Research And Engineering Company | Long life lubricating oil composition using particular detergent mixture |
-
2004
- 2004-06-03 US US10/861,601 patent/US20050054543A1/en not_active Abandoned
- 2004-08-19 CA CA002537266A patent/CA2537266A1/en not_active Abandoned
- 2004-08-19 EP EP04781798A patent/EP1668101A1/en not_active Withdrawn
- 2004-08-19 WO PCT/US2004/027184 patent/WO2005026301A1/en active Application Filing
- 2004-08-19 BR BRPI0413688-8A patent/BRPI0413688A/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0528610A1 (en) * | 1991-08-09 | 1993-02-24 | Oronite Japan Limited | Low phosphorous engine oil composition and additive compositions |
EP0588561A1 (en) * | 1992-09-14 | 1994-03-23 | Oronite Japan Limited | Low phosphorous engine oil compositions and additive compositions |
US5672572A (en) * | 1993-05-27 | 1997-09-30 | Arai; Katsuya | Lubricating oil composition |
EP0860495A2 (en) * | 1997-02-03 | 1998-08-26 | Tonen Corporation | Lubricating oil composition |
EP1104800A2 (en) * | 1999-12-02 | 2001-06-06 | Oronite Japan Limited | Lubricating oil composition for gas engines |
EP1418220A2 (en) * | 2002-10-31 | 2004-05-12 | Chevron Oronite Company LLC | A low-phosphorus lubricating oil composition for extended drain intervals |
Also Published As
Publication number | Publication date |
---|---|
US20050054543A1 (en) | 2005-03-10 |
BRPI0413688A (en) | 2006-10-24 |
EP1668101A1 (en) | 2006-06-14 |
CA2537266A1 (en) | 2005-03-24 |
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