US20120202728A1 - Lubricating composition - Google Patents
Lubricating composition Download PDFInfo
- Publication number
- US20120202728A1 US20120202728A1 US13/500,645 US201013500645A US2012202728A1 US 20120202728 A1 US20120202728 A1 US 20120202728A1 US 201013500645 A US201013500645 A US 201013500645A US 2012202728 A1 US2012202728 A1 US 2012202728A1
- Authority
- US
- United States
- Prior art keywords
- lubricating composition
- detergent
- amine compound
- composition according
- present
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 98
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 52
- 239000003599 detergent Substances 0.000 claims abstract description 56
- 239000002199 base oil Substances 0.000 claims abstract description 43
- -1 amine compound Chemical class 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000010710 diesel engine oil Substances 0.000 claims description 2
- 101100294102 Caenorhabditis elegans nhr-2 gene Proteins 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 10
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 229920013639 polyalphaolefin Polymers 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 6
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000010727 cylinder oil Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001509 aspartic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- 229960001860 salicylate Drugs 0.000 description 2
- 150000003873 salicylate salts Chemical class 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- 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
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
-
- 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
- C10M2207/26—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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/26—Amines
-
- 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
- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- 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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- 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
- C10N2030/52—Base number [TBN]
-
- 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
- C10N2040/252—Diesel engines
Definitions
- the present invention relates to a lubricating composition, in particular to lubricating compositions for use in internal combustion engines operated under sustained high load conditions, such as marine diesel engines and power applications. More particularly, the present invention relates to a marine cylinder oil.
- WO 2008/043901 A2 discloses a cylinder lubricant for a two-stroke marine engine, having a Base Number (according to ASTM D 2986) of at least 40 mg KOH/g, and containing form 0.01 to 1.0 wt. % of a primary, secondary or tertiary mono-alcohol having at least 12 carbon atoms.
- Lubricating compositions for use in internal combustion engines are subject to high levels of stress. It is important that the lubricating oil provides good lubrication properties under a variety of conditions, and amongst other properties, provides good wear, corrosion protection, help to keep the engine clean, be thermally and oxidatively stable and carry heat away from the engine.
- Lubricating compositions used in marine diesel engines are subject to particularly high levels of stress due to the fact that marine engines are usually run continuously at near full load conditions for long periods of time.
- marine does not restrict such engines to those used in water-borne vessels. That is to say, in addition said term also includes engines used for power generation applications. These highly rated, fuel efficient, slow- and medium-speed marine and stationary diesel engines operate at high pressures, high temperatures and long-strokes.
- a lubricating composition comprising:
- R 1 represents a hydrocarbyl group containing 1 to 50 carbon atoms and R 2 is selected from the group consisting of a hydrogen atom (H) and a hydrocarbyl group containing 1 to 50 carbon atoms; wherein the amine compound is present at a level of greater than 0.3 wt %, by weight of the lubricating composition.
- WO 2008/095966 discloses an industrial oil composition, such as a hydraulic fluid, comprising a base oil, an aspartic acid derivative and an aliphatic amine compound. As indicated on page 12, line 9, the composition may include a detergent-dispersant. Apart from the fact that no actual examples containing a detergent are disclosed in WO 2008/095966, it is to be noted that industrial oil compositions (typically not containing a large amount of detergent) differ substantially from the engine oils according to the present invention. As an example, the lubricating composition according to the present invention does preferably not contain an aspartic acid derivative.
- the lubricating compositions according to the present invention exhibit improved corrosive wear protection and/or BN retention and/or BN usage properties.
- base oil used in lubricating composition according to the present invention there are no particular limitations regarding the base oil used in lubricating composition according to the present invention, and various conventional mineral oils, synthetic oils as well as naturally derived esters such as vegetable oils may be conveniently used.
- the base oil used in the present invention may conveniently comprise mixtures of one or more mineral oils and/or one or more synthetic oils; thus, according to the present invention, the term “base oil” may refer to a mixture containing more than one base oil.
- Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
- Suitable base oils for use in the lubricating oil composition of the present invention are Group I-III mineral base oils, Group IV poly-alpha olefins (PAOs), Group I-III Fischer-Tropsch derived base oils and mixtures thereof.
- Group I lubricating oil base oils according to the definitions of American Petroleum Institute (API) for categories I-IV. These API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
- API American Petroleum Institute
- Fischer-Tropsch derived base oils are known in the art.
- Fischer-Tropsch derived is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process.
- a Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To-Liquids) base oil.
- Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.
- Synthetic oils include hydrocarbon oils such as olefin oligomers (including polyalphaolefin base oils; PA0s), dibasic acid esters, polyol esters, polyalkylene glycols (PAGs), alkyl naphthalenes and dewaxed waxy isomerates.
- hydrocarbon oils such as olefin oligomers (including polyalphaolefin base oils; PA0s), dibasic acid esters, polyol esters, polyalkylene glycols (PAGs), alkyl naphthalenes and dewaxed waxy isomerates.
- Synthetic hydrocarbon base oils sold by the Shell Group under the designation “Shell XHVI” (trade mark) may be conveniently used.
- Poly-alpha olefin base oils PAOs
- Preferred poly-alpha olefin base oils that may be used in the lubricating compositions of the present invention may be derived from linear C 2 to C 32 , preferably C 6 to C 16 , alpha olefins.
- Particularly preferred feedstocks for said poly-alpha olefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.
- the total amount of base oil incorporated in the lubricating composition of the present invention is preferably present in an amount in the range of from 60 to 99 wt. %, more preferably in an amount in the range of from 65 to 98 wt. % and most preferably in an amount in the range of from 70 to 95 wt. %, with respect to the total weight of the lubricating composition.
- detergents there are no particular limitations regarding the detergent as used in lubricating composition according to the present invention and various conventional detergents or mixtures thereof may be conveniently used.
- detergents that may be used include oil-soluble neutral and over-based sulphonates, phenates, sulphurized phenates, thiophosphonates, salicylates and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, and in particular calcium and magnesium.
- Preferred metal detergents are neutral and over-based detergents having a TBN (Total Base Number; according to ASTM D2896) of from 20 to 450. Combinations of detergents, whether over-based or neutral or both, may be used.
- the amount of the detergent in the compositions of the invention is typically from 0.01 wt. % to 35.0 wt. %, based on the total weight of the lubricating composition.
- the composition comprises at least 4 wt. % of the detergent, based on the total weight of the composition.
- the composition comprises at least 6 wt. %, more preferably 8 wt. %, even more preferably at least 10 wt. %, most preferably at least 15 wt. % of the detergent, based on the total weight of the composition.
- the detergent is a selected from a sulphonate-type detergent, a phenate detergent, or a mixture thereof.
- Sulphonate-type and phenate-type detergents are well known in the art.
- the amine compound having the general formula (I) as defined above may include a broad range of compounds.
- R 1 represents a hydrocarbyl group containing 1 to 50 carbon atoms and R 2 represents H or a hydrocarbyl group containing 8 to 30 carbon atoms.
- the hydrocarbyl groups of R 1 and R 2 may be saturated or unsaturated and linear or branched, they are preferably saturated carbon chains and preferably linear (thus unbranched).
- R 1 and R 2 (if R 2 does not represent H) both independently represent a hydrocarbyl group containing 4 to 40 carbon atoms and more preferably 8 to 30 carbon atoms, even more preferably 10 to 24 carbon atoms, most preferably 12 to 18 carbon atoms.
- R 2 in general formula (I) represents H.
- the amine compound is a primary amine having the following general formula (II): R 1 NH 2 (II).
- R 1 represents a hydrocarbyl group containing 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms, more preferably 12 to 18 carbon atoms.
- Especially preferred primary amines are n-dodecylamine (laurylamine), n-tridecylamine, n-tetradecylamine (myristylamine), n-pentadecylamine, n-hexadecylamine (n-palmitylamine), n-heptadecylamine and n-octadecylamine (n-stearylamine).
- the amount of the amine compound in the composition of the invention is greater than 0.3 wt % and preferably less than 2.5 wt %, preferably in the range of from 0.4 wt % to 2.4 wt. %, more preferably in the range from 0.5 to 2.0 wt. %, and especially in the range of from 1.0 wt % to 2.0 wt %, based on the total weight of the lubricating composition.
- the lubricating composition according to the present invention may further comprise one or more other additives such as anti-oxidants, anti-wear additives, dispersants, other detergents, extreme pressure additives, other friction modifiers, viscosity modifiers, pour point depressants, metal passivators, corrosion inhibitors, demulsifiers, anti-foam agents, seal compatibility agents and additive diluent base oils, etc.
- the lubricating composition according to the present contains less than 5.0 wt. %, more preferably less than 4.0 wt. % or even less than 3.0 wt. % of any other additives than one or more detergents, one or more dispersants and one or more amine compound(s) having general formula (I).
- the composition contains no other additives than one or more detergents, one or more dispersants and one or more amine compound(s) having general formula (I).
- the above-mentioned additives are typically present in an amount in the range of from 0.01 to 35.0 wt. %, based on the total weight of the lubricating composition, preferably in an amount in the range of from 5.0 to 30.0 wt. %, based on the total weight of the lubricating composition.
- the composition has a Total Base Number (TBN) value of at most 75 mg KOH/g, preferably at most 70 mg KOH/g, more preferably at most 65 mg KOH/g, even more preferably at most 60 mg KOH/g (in particular according to ASTM D 2896).
- TBN Total Base Number
- the composition has a total base number (TBN) value (according to ASTM D 2896) of above 20.0 mg KOH/g.
- the composition has a kinematic viscosity at 100° C. of above 5.6 mm 2 /s and below 21.9 mm 2 /s, preferably above 12.5 mm 2 /s, more preferably above 14.3 mm 2 /s, in particular according to ASTM D 445.
- the lubricating compositions of the present invention may be conveniently prepared by admixing the one or more additives with the base oil(s).
- the present invention provides the use of a lubricating composition according to the present invention, in order to improve one or more of corrosive wear protection properties (in particular according to the below described procedure based on ASTM G181) and BN retention properties (in particular as measured according to ASTM D 2896). Further, the present invention provides the use of a lubricating composition according to the present invention, in order to improve BN retention properties, whilst maintaining corrosive wear protection properties.
- the lubricating compositions according to the present invention are useful for lubricating apparatus generally, but in particular for use as engine oils for internal combustion engines.
- engine oils include passenger car engines, diesel engines, marine diesel engines, gas engines, two- and four-cycle engines, etc., and in particular marine diesel engines.
- Table 1 indicates the composition and properties of the formulations that were tested; the amounts of the components are given in wt. %, based on the total weight of the fully formulated formulations.
- All the tested marine cylinder oil formulations contained a combination of a base oil, a detergent additive package and—if present—a fatty amine or a fatty alcohol.
- the detergent additive packages contained a combination of neutral and over-based detergents.
- Base oil 1 was a commercially available Group I base oil blend having a kinematic viscosity at 100° C. (ASTM D445) of approx. 16 cSt (mm 2 s ⁇ 1 ). This base oil blend is commercially available from e.g. Shell Chemicals Ltd. (London, UK) under the trade designation “Catenex”.
- Base oil 2 was a base oil blend containing a thickener and 75 wt. % of a Group II base oil; the blend is commercially available from Chevron Products Company (San Ramon, Calif., USA) under the trade designation “Chevron 600 R”.
- Detergent package 1 was a salicylate-type detergent package.
- Detergent package 1 is commercially available from e.g. Infineum UK Ltd, (Abingdon, UK) under the trade designation “Infineum M”.
- Detergent package 2 “Detergent package 3” and “Detergent package 4” were blends of phenate-type and sulphonate-type detergents.
- Detergent packages 2, 3 and 4 components are commercially available from e.g. Chevron Oronite (Windsor, UK) under the trade designations “OLOA 219C” ,“OLOA 249SX” and “OLOA 246S” respectively.
- “Amine 1” was a n-hexadecylamine. Amine 1 is commercially available from e.g. Sigma-Aldrich (St. Louis, USA) under the trade designation “445312 (Aldrich)”.
- Amine 2 was a n-docecylamine. Amine 2 is commercially available from e.g. Sigma-Aldrich (St. Louis, USA) under the trade designation “D3629 (Sigma)”. “Alcohol 1” was a n-octadecanol. Alcohol 1 is commercially available from e.g. Merck KGaA (Darmstadt, Germany) under the trade designation “807680 Stearyl alcohol”.
- Alcohol 2 was a n-hexadecanol. Alcohol 2 is commercially available from e.g. Merck KGaA (Darmstadt, Germany) under the trade designation “818704 Cetyl alcohol”.
- compositions of Examples 1-10 and Comparative Examples 1-10 were obtained by mixing the base oils with the detergent, amine and/or alcohol using conventional lubricant blending procedures.
- Base oil 1 71.0 72.6 69.5 77.9 71.0 71.0 72.6 (Group I) Base oil 2 — — — — — — — — (Group II) Detergent package 1 29.0 — — — 28.0 28.0 — (salicylate) Detergent package 2 — 27.4 25.5 11.2 — — 26.4 (phenate + sulphonate) Detergent package 3 — — 5.0 10.9 — — — (phenate + sulphonate) Detergent package 4 — — — — — — — — (phenate + sulphonate) Amine 1 — — — — — — — (n-hexadecylamine) Amine 2 — — — — — — — (n-dodecylamine) Alcohol 1 — — — — — — 1.0 — 1.0 (n-octadecanol) Alcohol 2
- the normalised corrosive wear is the measured total wear [ ⁇ m] divided by the measured wear for the selected Comparative Example (based on the same detergent formulation).
- Examples 1 and 2 and Comparative Examples 5 and 6 are compared to Comparative Example 1 (and therefore the normalised wear for Comp. Ex. 1 is 1.00);
- Examples 3 and 4 and Comp. Ex. 7 are compared to Comp. Ex. 2.;
- Examples 5 and 6 are compared to Comp. Ex. 3;
- Examples 7 and 8 are compared to Comp. Ex. 4.
- Examples 9 and 10 are compared to Comparative Examples 8, 9 and 10.
- Examples 1-4 and 8 which contain a base oil and one or more detergents but no amine compound; more specifically, the presence of the amine compound in the Examples according to the present invention resulted in a lower consumed BN (and thus better BN retention), optimal use of the consumed fraction of BN (i.e. improved BN usage) and lower Total and Normalised corrosive wear.
- Comparative Examples 3 and 4 showed desirable consumed BN values, they exhibited much worse corrosive wear data (see e.g. Total corrosive wear).
- TBN levels of 40 (Examples 7 and 8) and 55 (Examples 5 and 6) in combination with amines resulted in a total wear value that is comparable with or less than (i.e. improved) those of Comparative Examples 1 and 2.
- a composition having a relatively low TBN (e.g. 40 or 55) but containing amines will perform equal or better in corrosive wear protection when compared to a composition having a relatively high TBN (e.g. 70) without amines, providing a route to formulate lower BN products as alternative for existing commercial 70 BN marine cylinder lubricants.
- Comparative Examples 8-10 and Examples 9 and 10 that a level of greater than 0.3 wt % of amine compound provides significantly lower corrosive wear.
- Comparative Examples 9 and 10 (containing only 0.2 wt % and 0.3 wt % amine, respectively) had a total corrosive wear of 232 ⁇ m and 239 ⁇ m, respectively, while Examples 9 and 10 (containing 0.5 wt % and 1.0 wt % of amine, respectively) had a total corrosive wear of 195 ⁇ m and 180 ⁇ m, respectively.
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Abstract
The present invention provides a lubricating composition comprising:—a base Oil;—a detergent; and—an amine compound having the following general formula (I): R 1 NHR 2 (I) wherein R1 represents a hydrocarbyl group containing 1 to 50 carbon atoms and R2 is selected from the group consisting of H and a hydrocarbyl group containing 1 to 50 carbon atoms; wherein the amine compound is present at a level of greater than 0.3 wt % by weight of the lubricating composition.
Description
- The present invention relates to a lubricating composition, in particular to lubricating compositions for use in internal combustion engines operated under sustained high load conditions, such as marine diesel engines and power applications. More particularly, the present invention relates to a marine cylinder oil.
- Marine cylinder oils are known in the art. As an example, WO 2008/043901 A2 discloses a cylinder lubricant for a two-stroke marine engine, having a Base Number (according to ASTM D 2986) of at least 40 mg KOH/g, and containing form 0.01 to 1.0 wt. % of a primary, secondary or tertiary mono-alcohol having at least 12 carbon atoms.
- Lubricating compositions for use in internal combustion engines are subject to high levels of stress. It is important that the lubricating oil provides good lubrication properties under a variety of conditions, and amongst other properties, provides good wear, corrosion protection, help to keep the engine clean, be thermally and oxidatively stable and carry heat away from the engine.
- Lubricating compositions used in marine diesel engines are subject to particularly high levels of stress due to the fact that marine engines are usually run continuously at near full load conditions for long periods of time.
- It will be appreciated in the art that the term “marine” does not restrict such engines to those used in water-borne vessels. That is to say, in addition said term also includes engines used for power generation applications. These highly rated, fuel efficient, slow- and medium-speed marine and stationary diesel engines operate at high pressures, high temperatures and long-strokes.
- It is an object of the present invention to improve the corrosive wear protection and BN retention properties of a lubricating composition, especially for use in an internal combustion engine such as a marine diesel engine.
- It is another object of the present invention to provide alternative lubricating compositions for use in an internal combustion engine.
- One or more of the above or other objects can be obtained by the present invention by providing a lubricating composition comprising:
- a base oil;
- a detergent; and
- an amine compound having the following general formula (I):
-
R1NHR2 (I) - wherein R1 represents a hydrocarbyl group containing 1 to 50 carbon atoms and R2 is selected from the group consisting of a hydrogen atom (H) and a hydrocarbyl group containing 1 to 50 carbon atoms; wherein the amine compound is present at a level of greater than 0.3 wt %, by weight of the lubricating composition.
- In this respect it is noted that WO 2008/095966 discloses an industrial oil composition, such as a hydraulic fluid, comprising a base oil, an aspartic acid derivative and an aliphatic amine compound. As indicated on page 12, line 9, the composition may include a detergent-dispersant. Apart from the fact that no actual examples containing a detergent are disclosed in WO 2008/095966, it is to be noted that industrial oil compositions (typically not containing a large amount of detergent) differ substantially from the engine oils according to the present invention. As an example, the lubricating composition according to the present invention does preferably not contain an aspartic acid derivative.
- It has now surprisingly been found according to the present invention that the lubricating compositions according to the present invention exhibit improved corrosive wear protection and/or BN retention and/or BN usage properties.
- There are no particular limitations regarding the base oil used in lubricating composition according to the present invention, and various conventional mineral oils, synthetic oils as well as naturally derived esters such as vegetable oils may be conveniently used.
- The base oil used in the present invention may conveniently comprise mixtures of one or more mineral oils and/or one or more synthetic oils; thus, according to the present invention, the term “base oil” may refer to a mixture containing more than one base oil. Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
- Suitable base oils for use in the lubricating oil composition of the present invention are Group I-III mineral base oils, Group IV poly-alpha olefins (PAOs), Group I-III Fischer-Tropsch derived base oils and mixtures thereof.
- By “Group I”, “Group II”, “Group III” and “Group IV” base oils in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum Institute (API) for categories I-IV. These API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
- Fischer-Tropsch derived base oils are known in the art. By the term “Fischer-Tropsch derived” is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process. A Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To-Liquids) base oil. Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.
- Synthetic oils include hydrocarbon oils such as olefin oligomers (including polyalphaolefin base oils; PA0s), dibasic acid esters, polyol esters, polyalkylene glycols (PAGs), alkyl naphthalenes and dewaxed waxy isomerates. Synthetic hydrocarbon base oils sold by the Shell Group under the designation “Shell XHVI” (trade mark) may be conveniently used.
- Poly-alpha olefin base oils (PAOs) and their manufacture are well known in the art. Preferred poly-alpha olefin base oils that may be used in the lubricating compositions of the present invention may be derived from linear C2 to C32, preferably C6 to C16, alpha olefins. Particularly preferred feedstocks for said poly-alpha olefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.
- The total amount of base oil incorporated in the lubricating composition of the present invention is preferably present in an amount in the range of from 60 to 99 wt. %, more preferably in an amount in the range of from 65 to 98 wt. % and most preferably in an amount in the range of from 70 to 95 wt. %, with respect to the total weight of the lubricating composition.
- There are no particular limitations regarding the detergent as used in lubricating composition according to the present invention and various conventional detergents or mixtures thereof may be conveniently used. Examples of detergents that may be used include oil-soluble neutral and over-based sulphonates, phenates, sulphurized phenates, thiophosphonates, salicylates and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, and in particular calcium and magnesium. Preferred metal detergents are neutral and over-based detergents having a TBN (Total Base Number; according to ASTM D2896) of from 20 to 450. Combinations of detergents, whether over-based or neutral or both, may be used.
- The amount of the detergent in the compositions of the invention is typically from 0.01 wt. % to 35.0 wt. %, based on the total weight of the lubricating composition. According to a preferred embodiment of the present invention, the composition comprises at least 4 wt. % of the detergent, based on the total weight of the composition. Preferably the composition comprises at least 6 wt. %, more preferably 8 wt. %, even more preferably at least 10 wt. %, most preferably at least 15 wt. % of the detergent, based on the total weight of the composition.
- Further it is preferred that the detergent is a selected from a sulphonate-type detergent, a phenate detergent, or a mixture thereof. Sulphonate-type and phenate-type detergents are well known in the art.
- The amine compound having the general formula (I) as defined above may include a broad range of compounds. As mentioned above, R1 represents a hydrocarbyl group containing 1 to 50 carbon atoms and R2 represents H or a hydrocarbyl group containing 8 to 30 carbon atoms. Although the hydrocarbyl groups of R1 and R2 may be saturated or unsaturated and linear or branched, they are preferably saturated carbon chains and preferably linear (thus unbranched). Preferably, R1 and R2 (if R2 does not represent H) both independently represent a hydrocarbyl group containing 4 to 40 carbon atoms and more preferably 8 to 30 carbon atoms, even more preferably 10 to 24 carbon atoms, most preferably 12 to 18 carbon atoms.
- Preferably, R2 in general formula (I) represents H. In the latter case, the amine compound is a primary amine having the following general formula (II): R1NH2 (II).
- Further, it is preferred that, in general formula (I) or (II) above, R1 represents a hydrocarbyl group containing 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms, more preferably 12 to 18 carbon atoms. Especially preferred primary amines are n-dodecylamine (laurylamine), n-tridecylamine, n-tetradecylamine (myristylamine), n-pentadecylamine, n-hexadecylamine (n-palmitylamine), n-heptadecylamine and n-octadecylamine (n-stearylamine).
- The amount of the amine compound in the composition of the invention is greater than 0.3 wt % and preferably less than 2.5 wt %, preferably in the range of from 0.4 wt % to 2.4 wt. %, more preferably in the range from 0.5 to 2.0 wt. %, and especially in the range of from 1.0 wt % to 2.0 wt %, based on the total weight of the lubricating composition.
- The lubricating composition according to the present invention may further comprise one or more other additives such as anti-oxidants, anti-wear additives, dispersants, other detergents, extreme pressure additives, other friction modifiers, viscosity modifiers, pour point depressants, metal passivators, corrosion inhibitors, demulsifiers, anti-foam agents, seal compatibility agents and additive diluent base oils, etc. However, preferably, the lubricating composition according to the present contains less than 5.0 wt. %, more preferably less than 4.0 wt. % or even less than 3.0 wt. % of any other additives than one or more detergents, one or more dispersants and one or more amine compound(s) having general formula (I). Preferably, the composition contains no other additives than one or more detergents, one or more dispersants and one or more amine compound(s) having general formula (I).
- As the person skilled in the art is familiar with the above and other additives, these are not further discussed here in detail. Specific examples of such additives are described in for example Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pages 477-526.
- The above-mentioned additives are typically present in an amount in the range of from 0.01 to 35.0 wt. %, based on the total weight of the lubricating composition, preferably in an amount in the range of from 5.0 to 30.0 wt. %, based on the total weight of the lubricating composition.
- Preferably, the composition has a Total Base Number (TBN) value of at most 75 mg KOH/g, preferably at most 70 mg KOH/g, more preferably at most 65 mg KOH/g, even more preferably at most 60 mg KOH/g (in particular according to ASTM D 2896). Typically, the composition has a total base number (TBN) value (according to ASTM D 2896) of above 20.0 mg KOH/g.
- Further it is preferred according to the present invention that the composition has a kinematic viscosity at 100° C. of above 5.6 mm2/s and below 21.9 mm2/s, preferably above 12.5 mm2/s, more preferably above 14.3 mm2/s, in particular according to ASTM D 445.
- The lubricating compositions of the present invention may be conveniently prepared by admixing the one or more additives with the base oil(s).
- In another aspect, the present invention provides the use of a lubricating composition according to the present invention, in order to improve one or more of corrosive wear protection properties (in particular according to the below described procedure based on ASTM G181) and BN retention properties (in particular as measured according to ASTM D 2896). Further, the present invention provides the use of a lubricating composition according to the present invention, in order to improve BN retention properties, whilst maintaining corrosive wear protection properties.
- The lubricating compositions according to the present invention are useful for lubricating apparatus generally, but in particular for use as engine oils for internal combustion engines. These engine oils include passenger car engines, diesel engines, marine diesel engines, gas engines, two- and four-cycle engines, etc., and in particular marine diesel engines.
- The present invention is described below with reference to the following Examples, which are not intended to limit the scope of the present invention in any way.
- Various lubricating compositions for use as marine cylinder oils in a marine diesel engine were formulated. Table 1 indicates the composition and properties of the formulations that were tested; the amounts of the components are given in wt. %, based on the total weight of the fully formulated formulations.
- All tested marine diesel engine oil formulations were formulated as SAE 40 or SAE 50 formulations meeting the so-called SAE J300 Specifications (as revised in January 2009; SAE stands for Society of Automotive Engineers).
- All the tested marine cylinder oil formulations contained a combination of a base oil, a detergent additive package and—if present—a fatty amine or a fatty alcohol. The detergent additive packages contained a combination of neutral and over-based detergents.
- “Base oil 1” was a commercially available Group I base oil blend having a kinematic viscosity at 100° C. (ASTM D445) of approx. 16 cSt (mm2s−1). This base oil blend is commercially available from e.g. Shell Chemicals Ltd. (London, UK) under the trade designation “Catenex”.
- “Base oil 2” was a base oil blend containing a thickener and 75 wt. % of a Group II base oil; the blend is commercially available from Chevron Products Company (San Ramon, Calif., USA) under the trade designation “Chevron 600 R”.
- “Detergent package 1” was a salicylate-type detergent package. Detergent package 1 is commercially available from e.g. Infineum UK Ltd, (Abingdon, UK) under the trade designation “Infineum M”.
- “Detergent package 2”, “Detergent package 3” and “Detergent package 4” were blends of phenate-type and sulphonate-type detergents. Detergent packages 2, 3 and 4 components are commercially available from e.g. Chevron Oronite (Windsor, UK) under the trade designations “OLOA 219C” ,“OLOA 249SX” and “OLOA 246S” respectively. “Amine 1” was a n-hexadecylamine. Amine 1 is commercially available from e.g. Sigma-Aldrich (St. Louis, USA) under the trade designation “445312 (Aldrich)”.
- “Amine 2” was a n-docecylamine. Amine 2 is commercially available from e.g. Sigma-Aldrich (St. Louis, USA) under the trade designation “D3629 (Sigma)”. “Alcohol 1” was a n-octadecanol. Alcohol 1 is commercially available from e.g. Merck KGaA (Darmstadt, Germany) under the trade designation “807680 Stearyl alcohol”.
- “Alcohol 2” was a n-hexadecanol. Alcohol 2 is commercially available from e.g. Merck KGaA (Darmstadt, Germany) under the trade designation “818704 Cetyl alcohol”.
- The compositions of Examples 1-10 and Comparative Examples 1-10 were obtained by mixing the base oils with the detergent, amine and/or alcohol using conventional lubricant blending procedures.
-
TABLE 1 Component [wt. %] Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Base oil 1 71.0 71.0 72.6 72.6 69.5 69.5 77.9 77.9 (Group I) Base oil 2 — — — — — — — — (Group II) Detergent package 1 28.0 28.0 — — — — — — (salicylate) Detergent package 2 — — 26.4 26.4 24.5 25.0 10.2 10.7 (phenate + sulphonate) Detergent package 3 — — — — 5.0 5.0 10.9 10.9 (phenate + sulphonate) Detergent package 4 — — — — — — — — (phenate + sulphonate) Amine 1 1.0 — 1.0 — 1.0 0.5 1.0 0.5 (n-hexadecylamine) Amine 2 — 1.0 — 1.0 — — — — (n-dodecylamine) Alcohol 1 — — — — — — — — (n-octadecanol) Alcohol 2 — — — — — — — — (n-hexadecanol) TOTAL 100 100 100 100 100 100 100 100 Properties of the formulated lubricating composition TBN value1 [mg KOH/g] 71.28 71.96 72.69 73.55 57.64 56.70 42.64 42.11 Kinematic viscosity at 19.78 19.62 18.75 18.56 19.40 19.42 19.24 19.27 100° C.2 [cSt] Kinematic viscosity at 200.5 199.4 209.1 207.1 230.1 229.5 228.5 227.6 40° C.2 [cSt] Component Comp. Comp. Comp. Comp. Comp. Comp. Comp. [wt. %] Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Base oil 1 71.0 72.6 69.5 77.9 71.0 71.0 72.6 (Group I) Base oil 2 — — — — — — — (Group II) Detergent package 1 29.0 — — — 28.0 28.0 — (salicylate) Detergent package 2 — 27.4 25.5 11.2 — — 26.4 (phenate + sulphonate) Detergent package 3 — — 5.0 10.9 — — — (phenate + sulphonate) Detergent package 4 — — — — — — — (phenate + sulphonate) Amine 1 — — — — — — — (n-hexadecylamine) Amine 2 — — — — — — — (n-dodecylamine) Alcohol 1 — — — — 1.0 — 1.0 (n-octadecanol) Alcohol 2 — — — — — 1.0 — (n-hexadecanol) TOTAL 100 100 100 100 100 100 100 Properties of the formulated lubricating composition TBN value1 [mg KOH/g] 73.01 70.67 55.56 41.41 69.35 69.19 71.11 Kinematic viscosity at 19.62 19.43 19.42 19.28 19.14 19.61 18.84 100° C.2 [cSt] Kinematic viscosity at 197.9 220.4 228.2 225.7 193.1 191.9 209.3 40° C.2 [cSt] Component Comp. Comp. Comp. [wt. %] Ex. 8 Ex. 9 Ex. 10 Ex. 9 Ex. 10 Base oil 1 — — — — — (Group I) Base oil 2 78.0 78.0 78.0 78.0 78.0 (Group II) Detergent package 1 — — — — — (salicylates) Detergent package 2 — — — — — (phenate + sulphonate) Detergent package 3 — — — — — (phenate + sulphonate) Detergent package 4 22.0 22.0 22.0 22.0 22.0 (phenate + sulphonate) Amine 1 — 0.2 0.3 0.5 1.0 (n-hexadecylamine) Amine 2 — — — — — (n-dodecylamine) Alcohol 1 — — — — — (n-octadecanol) Alcohol 2 — — — — — (n-hexadecanol) TOTAL 100 100 100 100 100 Properties of the formulated lubricating composition TBN value1 [mg KOH/g] 58.4 58.83 59.15 59.56 60.67 Kinematic viscosity at 15.36 15.28 15.24 15.15 14.85 100° C.2 [cSt] Kinematic viscosity at 142.5 141.1 140.4 138.8 136.5 40° C.2 [cSt] 1According to ASTM D 2896; 2According to ASTM D 445 - In order to demonstrate the corrosive wear protection properties of the present invention, measurements were performed with a corrosive procedure based on the standard ASTM G181 test (“Standard practice for conducting friction tests of piston ring and cylinder liner materials under lubricated conditions”) for determining corrosive wear whilst using the well-known Plint TE-77 Reciprocating Test Rig (available from Phoenix Tribology Ltd, Newbury, UK) in which a moving specimen is reciprocated against a stationary plate to simulate piston top position under closely controlled conditions. As test specimen a steel plate (Steel 20 RC, annealed) and a pin finely machined from a 2-stroke engine piston ring (Bolnes DNL 190/600) were used.
- During the test a lubricating oil feed rate of 0.05 ml/min was used; also an acid (acid strength: H2SO4 6N) feed rate of 0.05 ml/min over the contact surface on the plate was used, during 5 minutes each 10 minutes (i.e. 5 minutes off, 5 minutes on, 5 minutes off, etc.). In the test, the following test conditions were used:
- Load: 200 N
- Temperature: 180° C.
- Reciprocating Frequency: 10 Hz
- Stroke length: 15 mm
- Time: 60 minutes.
- The measured corrosive wear properties are indicated in Table 2 below.
-
TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 TBN value1 58.08 60.05 66.16 67.16 50.04 48.15 34.29 31.41 [mg KOH/g] Consumed BN2 [%] 18.51 16.55 8.98 8.69 13.18 15.08 19.58 25.41 Total corrosive wear3 221 192 117 146 118 191 155 210 [μm] Normalised corrosive 0.73 0.64 0.47 0.59 0.36 0.58 0.30 0.40 wear4 Comp. Comp. Comp. Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 TBN value1 53.50 55.01 44.68 35.92 53.36 52.43 55.59 [mg KOH/g] Consumed BN2 [%] 26.72 22.15 19.58 13.25 23.05 24.22 21.82 Total corrosive wear3 302 249 329 523 286 366 273 [μm] Normalised corrosive 1.00 1.00 1.00 1.00 0.95 1.21 1.10 wear4 Comp. Comp. Comp. Ex. 8 Ex. 9 Ex. 10 Ex. 9 Ex. 10 TBN value1 41.97 44.80 45.29 44.26 45.59 [mg KOH/g] Consumed BN2 [%] 28.13 23.85 23.43 25.69 24.86 Total corrosive wear3 246 232 239 195 180 [μm] Normalised corrosive 1.0 0.94 0.97 0.79 0.73 wear4 1According to ASTM D 2896, after test; 2Decrease of BN compared with TBN value before test (see Table 1); for Example 1 this is [(71.28-58.08)/71.28]*100% = 18.52; 3Total corrosive wear is the sum of wear scar depth on plate and pin height reduction. Wear scar depth on plate was measured with a depth gauge (Digimatic Indicator ID-H, available from Mitutoyo Corporation) and pin height reduction was measured with a micrometer (Absolute Digimatic Micrometer, available from Mitutoyo Corporation); 4The normalised corrosive wear is the measured total wear [μm] divided by the measured wear for the selected Comparative Example (based on the same detergent formulation). Examples 1 and 2 and Comparative Examples 5 and 6 are compared to Comparative Example 1 (and therefore the normalised wear for Comp. Ex. 1 is 1.00); Examples 3 and 4 and Comp. Ex. 7 are compared to Comp. Ex. 2.; Examples 5 and 6 are compared to Comp. Ex. 3; and Examples 7 and 8 are compared to Comp. Ex. 4. Examples 9 and 10 are compared to Comparative Examples 8, 9 and 10. - As can be learned from Table 2, the corrosive wear protection and BN retention properties for the compositions according to the present invention were significantly improved when compared with Comparative
- Examples 1-4 and 8, which contain a base oil and one or more detergents but no amine compound; more specifically, the presence of the amine compound in the Examples according to the present invention resulted in a lower consumed BN (and thus better BN retention), optimal use of the consumed fraction of BN (i.e. improved BN usage) and lower Total and Normalised corrosive wear. In this respect it is noted that although Comparative Examples 3 and 4 showed desirable consumed BN values, they exhibited much worse corrosive wear data (see e.g. Total corrosive wear).
- Also, it can be seen that the corrosive wear protection properties for the compositions according to the present invention were significantly improved when compared with Comparative Examples 5-7, which contain a base oil, one or more detergents and a primary fatty alcohol. In this respect it is noted that such primary fatty alcohols have been recently suggested (see WO 2008/043901) for the purpose of BN usage optimisation, meaning improved acid neutralisation properties and thus improved corrosive wear protection.
- From the comparison of the BN retention values of Examples 1 to 3 it can be learned that according to the present invention there is a preference for a mixture of a sulphonate-type and a phenate-type detergent (rather than a salicylate-type detergent); this, as Examples 3 and 4 exhibit a lower consumed BN and thus a better BN retention for the given 70 BN level.
- Furthermore, it can be learned from Examples 5 to 8 that TBN levels of 40 (Examples 7 and 8) and 55 (Examples 5 and 6) in combination with amines resulted in a total wear value that is comparable with or less than (i.e. improved) those of Comparative Examples 1 and 2. This surprisingly suggests that a composition having a relatively low TBN (e.g. 40 or 55) but containing amines will perform equal or better in corrosive wear protection when compared to a composition having a relatively high TBN (e.g. 70) without amines, providing a route to formulate lower BN products as alternative for existing commercial 70 BN marine cylinder lubricants.
- Furthermore, it can be learned from Comparative Examples 8-10 and Examples 9 and 10 that a level of greater than 0.3 wt % of amine compound provides significantly lower corrosive wear. Comparative Examples 9 and 10 (containing only 0.2 wt % and 0.3 wt % amine, respectively) had a total corrosive wear of 232 μm and 239 μm, respectively, while Examples 9 and 10 (containing 0.5 wt % and 1.0 wt % of amine, respectively) had a total corrosive wear of 195 μm and 180 μm, respectively.
Claims (14)
1. A lubricating composition comprising:
a base oil;
a detergent; and
an amine compound having the following general formula (I):
R1NHR2 (I)
R1NHR2 (I)
wherein R1 represents a hydrocarbyl group containing 1 to 50 carbon atoms and R2 is selected from the group consisting of H and a hydrocarbyl group containing 1 to 50 carbon atoms;
wherein the amine compound is present at a level of greater than 0.3 wt % and less than 2.5 wt %, by weight of the lubricating composition.
2. The lubricating composition according to claim 1 wherein the amine compound is present at a level in the range of from 0.4 wt % to 2.4 wt %, by weight of the lubricating composition.
3. The lubricating composition according to claim 1 wherein the amine compound is present at a level in the range of from 0.5 wt % to 2.0 wt %, by weight of the lubricating composition.
4. The lubricating composition according to claim 1 wherein R2 represents H.
5. The lubricating composition according to claim 1 wherein R1 represents a hydrocarbyl group containing 8 to 30 carbon atoms.
6. The lubricating composition according to claim 1 wherein the composition comprises from 0.01 wt. % to 2.0 wt. % of the amine compound having general formula (I), based on the total weight of the composition.
7. The lubricating composition according to claim 1 wherein the composition comprises at least 4 wt. % of the detergent.
8. The lubricating composition according to claim 1 wherein the detergent is selected from the group consisting of a sulphonate-type detergent, a phenate-type detergent, and mixtures.
9. The lubricating composition according to claim 1 wherein the composition has a Total Base Number (TBN) value of at most 75 mg KOH/g.
10. The lubricating composition according to claim 1 wherein the composition has a kinematic viscosity at 100° C. of above 5.6 mm2/s and below 21.9 mm2/s.
11. The lubricating composition according to claim 1 wherein the composition contains no other additives than one or more detergents, one or more dispersants and one or more amine compound(s) having general formula (I).
12. The lubricating composition according to claim 1 wherein the composition is a marine diesel engine oil.
13. A lubricating composition comprising:
a base oil;
a detergent; and
an amine compound having the following general formula (I):
R1NHR2 (I)
R1NHR2 (I)
wherein R1 represents a hydrocarbyl group containing 1 to 50 carbon atoms and R2 is selected from the group consisting of H and a hydrocarbyl group containing 1 to 50 carbon atoms;
wherein the amine compound is present at a level of greater than 0.3 wt %, by weight of the lubricating composition;
and wherein the composition has a Total Base Number (TBN) value of at most 65 mg KOH/g, even more preferably at most 60 mg KOH/g (in particular according to ASTM D 2896)
14. Use of a lubricating composition according to claim 13 in order to improve one or more of corrosive wear protection properties according to ASTM G181, BN retention and BN usage properties as measured according to ASTM D 2896.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09172633.1 | 2009-10-09 | ||
| EP09172633 | 2009-10-09 | ||
| PCT/EP2010/065129 WO2011042552A1 (en) | 2009-10-09 | 2010-10-08 | Lubricating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20120202728A1 true US20120202728A1 (en) | 2012-08-09 |
Family
ID=41666712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/500,645 Abandoned US20120202728A1 (en) | 2009-10-09 | 2010-10-08 | Lubricating composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20120202728A1 (en) |
| EP (1) | EP2486113B2 (en) |
| KR (1) | KR101722380B1 (en) |
| CN (1) | CN102549125B (en) |
| WO (1) | WO2011042552A1 (en) |
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| US20140051621A1 (en) * | 2012-08-14 | 2014-02-20 | Basf Se | Lubricant composition comprising unhindered alkyl amines |
| US20160289588A1 (en) * | 2013-11-04 | 2016-10-06 | Basf Se | Lubricant Composition |
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| US20220098508A1 (en) * | 2018-08-30 | 2022-03-31 | Basf Se | Lubricant composition |
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| CN106811266A (en) | 2009-10-26 | 2017-06-09 | 国际壳牌研究有限公司 | Lubricating composition |
| WO2012138733A2 (en) * | 2011-04-05 | 2012-10-11 | Chevron Oronite Company Llc | Low viscosity marine cylinder lubricating oil compositions |
| DK2767578T3 (en) * | 2013-02-19 | 2016-05-09 | Lukoil Marine Lubricants Germany Gmbh | A method and apparatus for producing a cylinder oil |
| FR3027607B1 (en) * | 2014-10-27 | 2018-01-05 | Total Marketing Services | LUBRICANT FOR MARINE ENGINE |
| FR3039835B1 (en) * | 2015-08-03 | 2019-07-05 | Total Marketing Services | USE OF A FATTY AMINE FOR PREVENTING AND / OR REDUCING METALLIC LOSS OF PARTS IN AN ENGINE |
| DK4055129T3 (en) | 2019-11-07 | 2024-08-26 | Totalenergies Onetech | LUBRICANT FOR A MARINE ENGINE |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20120093933A (en) | 2012-08-23 |
| CN102549125B (en) | 2014-09-24 |
| EP2486113B2 (en) | 2022-12-07 |
| EP2486113B1 (en) | 2015-01-21 |
| WO2011042552A1 (en) | 2011-04-14 |
| CN102549125A (en) | 2012-07-04 |
| KR101722380B1 (en) | 2017-04-05 |
| HK1174938A1 (en) | 2013-06-21 |
| EP2486113A1 (en) | 2012-08-15 |
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