EP1668101A1 - Long life lubricating oil composition using particular antioxidant components - Google Patents

Long life lubricating oil composition using particular antioxidant components

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Publication number
EP1668101A1
EP1668101A1 EP04781798A EP04781798A EP1668101A1 EP 1668101 A1 EP1668101 A1 EP 1668101A1 EP 04781798 A EP04781798 A EP 04781798A EP 04781798 A EP04781798 A EP 04781798A EP 1668101 A1 EP1668101 A1 EP 1668101A1
Authority
EP
European Patent Office
Prior art keywords
composition
volume
oil
ashless
alkylthiocarbamoyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04781798A
Other languages
German (de)
French (fr)
Inventor
Stanley James Cartwright
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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Filing date
Publication date
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1668101A1 publication Critical patent/EP1668101A1/en
Withdrawn legal-status Critical Current

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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—Overbased sulfonic 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

A natural gas engine oil composition with enhanced resistance to oxidation, nitration and viscosity increase comprising: an oil basestock; neutral and overbased metallic detergents; an antioxidant comprising an alkylthiocarbamoyl compound or a mixture of an aklylthiocarbamoyl compound and an ashless, non-sulfur containing, hindered phenol; and a zinc dihydrocarbyl dithiophosphate in an amount sufficient to provide the composition with from 250 to 450 wppm phosphorus.

Description

LONG LIFE LUBRICATING OIL COMPOSITION USING PARTICULAR ANTIOXIDANT COMPONENTS
Field of Invention [0001] 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.
Background of Invention [0002] 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 (NOx), 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.
[0003] Thus, it is desirable to extend the life of gas engine oils by enhancing the oil's resistance to oxidation and nitration and to reduce viscosity increases in the oil.
[0004] To extend lubricant life, base oils are formulated with various additives such as dispersants, detergents, antioxidants, viscosity index improvers and the like to provide a lubricating oil composition. This art of lubricating oil formulation, however, 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.
[0005] An object of the present invention is to provide a gas engine lubricating composition that has enhanced resistance to oxidation and nitration.
[0006] Another object of the invention is to provide a gas engine lubricating composition that has improved life as evidenced by reduction in viscosity increase.
Summary of Invention
[0007] Accordingly, a natural gas engine lubricant composition having enhanced resistance to oxidation, nitration and viscosity increase comprises:
(a) a major amount of an oil basestock of lubricating viscosity having a kinematic viscosity at 100°C of about 5 to 16 cSt and preferably about 10 to about 13 cSt;
(b) 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;
(c) a minor amount of an antioxidant comprising an alkylthiocarbamoyl compound or a mixture of an alkylthiocarbamoyl compound and an ashless, non-sulfur containing hindered phenol; and,
(d) a zinc dihydrocarbyl dithiophosphate in an amount sufficient to provide the lubricant composition with from 250 to 450 wppm of phosphorus. [0008] Other gas engine oil additives also may be present. These include: ashless dispersants, metal passivators, pour point depressants, VI improvers and antifoamants.
Detailed Description of the Invention [0009] 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. Typically, 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. Especially preferred are API category Group II basestocks.
[0010] 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. Preferably 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.
[0011] 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 %. Expressed in terms based on active ingredient in the detergent mixture, 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. [0012] The lubricating composition of the invention contains a minor but effective amount of an antioxidant comprising an alkylthiocarbamoyl compound or a mixture of an alkylthiocarbamoyl compound and an ashless, non-sulfur containing, hindered phenol. >
[0013] Suitable alkylthiocarbamoyl compounds are represented by the formula:
where R1, R2, R3 and R4 are the same or different linear and branched alkyl groups of from 1 to 18 carbon atoms, X is S, S-S, S-(CH2)y-S, S-CH2-CH(R5)-S; y is an integer of" 1 to 4, and R5 is an alkyl group of 1 to 2 carbons. Preferably R1, R2, R3 and R4 are C4 alkyl groups, X is S(CH2)yS, Y is 1-3.
[0014] 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.
[0015] In an alternate embodiment, the composition of the invention contains an antioxidant comprising a mixture of an alkylthiocarbamoyl compound and an ashless, sulfur free, hindered phenol. In this embodiment, 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
where Rl5 R2 and R3 are the same or different alkyl groups of 1 to 18 carbon atoms.
[0016] In the embodiment where 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 %.
[0017] 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. Preferably 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.
[0018] 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.
I
Examples and Coriiparative Examples
[0019] The in ention will be further illustrated by the following Examples and Comparative Examples.
[0020] 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.
[0021] Comparative Oil 1 is a low ash commercial gas engine oil which employed a commercial gas engine oil additive package.
[0022] 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.
[0023] 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.
Table 1
PPD = pour point depressant
[0024] As can be seen, 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.

Claims

CLAIMS:
1. A natural gas engine lubricating oil composition having enhanced resistance to oxidation, nitration and viscosity increase comprising: a major amount of an oil of lubricating viscosity; 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 mindr amount of an antioxidant comprising an alkylthiocarbamoyl compound or a mixture of an alkylthiocarbamoyl compound and an ashless, non- sulfur containing hindered phenol; and a zinc dihydrocarbyl dithiophosphate in an amount sufficient to provide the composition with from 250 to 450 wppm phosphorus.
2. The composition of claim 1 wherein the oil basestock has a kinematic viscosity at 100°C of about 5 to about 16 cSt.
3. The composition of claim 2 wherein, based on the total volume of the composition the detergents comprise from about 0.5 volume % to about 10 volume %.
4. The composition of claim 3 wherein the antioxidant is an alkylthiocarbamoyl compound which comprises about 0.25 volume % to about 2.0 volume % of the composition.
5. The composition of claim 3 wherein the antioxidant is a mixture of an alkylthiocarbamoyl compound and an ashless, non-sulfur containing hindered phenol, wherein the alkylthiocarbamoyl compound comprises 0.25 volume % to 1.5 volume % of the composition and the phenol, 0.25 volume % to 1.5 volume % of the compositiqn.
6. The composition of claim 4 or 5 wherein the alkylthiocarbamoyl compound is represented by the formula
where R1, R2, R3 and R4 are the same or different linear and branched alkyl groups of from 1 to 18 carbon atoms, X is S, S-S, S-(CH2)y-S, S-CH2-CH(R5)-S; y is an integer of 1 to 4, and R5 is an alkyl group of 1 to 2 carbons. Preferably R1, R2, R3 and R4 are C4 alkyl, X is S(CH2)yS, Y is 1-3.
7. The composition of claim 5 wherein the ashless, non-sulfur containing, hindered phenol is represented by the formulae:
; and
where Rl5 R2 and R3 are the same or different alkyl groups of 1 to 18 carbon atoms.
EP04781798A 2003-09-05 2004-08-19 Long life lubricating oil composition using particular antioxidant components Withdrawn EP1668101A1 (en)

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US7309681B2 (en) * 2003-05-02 2007-12-18 Exxonmobil Research And Engineering Company Ashless lubricating oil composition with long life
CN102224228A (en) * 2008-07-16 2011-10-19 卢布里佐尔公司 Improved lubricant for natural gas engines
US8841243B2 (en) 2010-03-31 2014-09-23 Chevron Oronite Company Llc Natural gas engine lubricating oil compositions

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JPS5911397A (en) * 1982-06-09 1984-01-20 Idemitsu Kosan Co Ltd Fatigue life modifying lubricant
JP3086727B2 (en) * 1991-08-09 2000-09-11 オロナイトジャパン株式会社 Additive composition for producing low phosphorus engine oil
DE69322344T2 (en) * 1992-09-14 1999-04-29 Oronite Japan Ltd., Tokio/Tokyo Low phosphorus engine oil compositions and additive compositions
US5672572A (en) * 1993-05-27 1997-09-30 Arai; Katsuya Lubricating oil composition
JP4028614B2 (en) * 1997-02-03 2007-12-26 東燃ゼネラル石油株式会社 Lubricating oil composition
JP2001158896A (en) * 1999-12-02 2001-06-12 Chevron Oronite Ltd Lubricating oil composition for internal combustion engine particularly effective for lubrication of gas engine
US6140282A (en) * 1999-12-15 2000-10-31 Exxonmobil Research And Engineering Company Long life lubricating oil composition using particular detergent mixture
US20040087451A1 (en) * 2002-10-31 2004-05-06 Roby Stephen H. Low-phosphorus lubricating oil composition for extended drain intervals

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