CA2471202C - Marine diesel cylinder lubricant composition - Google Patents
Marine diesel cylinder lubricant composition Download PDFInfo
- Publication number
- CA2471202C CA2471202C CA2471202A CA2471202A CA2471202C CA 2471202 C CA2471202 C CA 2471202C CA 2471202 A CA2471202 A CA 2471202A CA 2471202 A CA2471202 A CA 2471202A CA 2471202 C CA2471202 C CA 2471202C
- Authority
- CA
- Canada
- Prior art keywords
- marine diesel
- lubricant composition
- diesel cylinder
- cylinder lubricant
- mass
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 239000000314 lubricant Substances 0.000 title claims abstract description 62
- 239000003599 detergent Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 13
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229960001860 salicylate Drugs 0.000 claims abstract description 13
- 239000005864 Sulphur Substances 0.000 claims abstract description 12
- 230000001050 lubricating effect Effects 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims 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 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 235000006708 antioxidants Nutrition 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000000994 depressogenic effect Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000005461 lubrication Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 30
- 239000002585 base Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010687 lubricating oil Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- -1 I-propyl Chemical group 0.000 description 7
- 239000002199 base oil Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007866 anti-wear additive Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000010689 synthetic lubricating oil Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- KDUGNDDZXPJVCS-UHFFFAOYSA-N 6-oxo-6-tridecoxyhexanoic acid Chemical compound CCCCCCCCCCCCCOC(=O)CCCCC(O)=O KDUGNDDZXPJVCS-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NEHDRDVHPTWWFG-UHFFFAOYSA-N Dioctyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NEHDRDVHPTWWFG-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
- C10M2207/023—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
- C10M2215/24—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
- C10M2215/28—Amides; Imides
-
- 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
- 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
- C10N2010/04—Groups 2 or 12
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- 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
- C10N2030/04—Detergent property or dispersant property
-
- 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]
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- 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
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- 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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron
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- Lubricants (AREA)
Abstract
A marine diesel cylinder lubricant composition for a marine diesel engine running on fuel having a sulphur content of less than 1.5%, the composition having a total base number, as determined according to ASTM D2896, of more than 30 and less than 70, and comprising at least 40 wt% of an oil of lubricating viscosity, and at least one detergent prepared from at least two surfactants, one of which is a salicylate. The marine diesel cylinder lubricant composition demonstrates good ability to reduce deposit formation, especially on pistons. The marine diesel cylinder lubricant composition also demonstrates good lubrication at temperatures above 250°C.
Description
Marine Diesel Cylinder Lubricant Composition This invention concerns a lubricant composition, in particular, a marine diesel cylinder lubricant (MDCL) composition. Marine diesel cylinder lubricant compositions are total loss lubricants and their purpose is to provide a strong oil film between the cylinder liner and the piston rings and to neutralise acids formed by combustion of sulphur compounds in the fuel.
Fuels used for diesel engines generally have a high sulphur content, which results in exhaust gases from diesel engines containing large amounts of sulphur oxides (SO,). The sulphur oxides react with moisture also present in the exhaust gases to form sulphuric acid which corrodes the engine. Marine diesel cylinder lubricant compositions therefore include overbased metallic detergents to neutralise the sulphuric acid. Commercial marine diesel cylinder lubricant compositions generally have a total base number ('TBN') of at least 70 (as determined using ASTM D2896).
There is growing environmental pressure to reduce the amount of sulphur in fuels. Therefore, a marine diesel cylinder lubricant composition having a TBN
less than 70 could be used. However, the applicants have found that if a marine diesel cylinder lubricant composition is diluted with base oil to lower the total base number to less than 70, the ability of the lubricant to prevent deposit formation, particularly on the pistons, is significantly reduced.
The aim of the present invention is to provide a marine diesel cylinder lubricant composition having a base number lower than 70 without reducing the ability of the lubricant to prevent deposit formation, particularly on the pistons.
In accordance with the present invention there is provided a marine diesel cylinder lubricant composition for a marine diesel engine running on fuel having a sulphur content of less than 1.5%, the composition having a total base number, as determined according to ASTM D2896, of more than 30 and less than 70, and comprising:
- at least 40 wt% of an oil of lubricating viscosity, and - at least one detergent prepared from at least two surfactants, one of which is a salicylate.
The inventor has found that the marine diesel cylinder lubricant composition defined above is capable of preventing deposit formation, particularly on the pistons, and is also capable of improving resistance to high temperature-induced wear (i.e. scuffing).
The marine diesel cylinder lubricant composition has a total base number (TBN) of less than 70, preferably less than 60, and most preferably less than 50.
Furthermore, the marine diesel cylinder lubricant composition preferably has a total base number (TBN) of more than 32, more preferably more than 35.
In accordance with the present invention there is also provided a method of operating a marine diesel cylinder engine running on fuel having at most 1.5%
sulphur, the method including the step of using the marine diesel cylinder lubricant composition defined above to lubricate the engine.
In accordance with the present invention there is also provided use of the marine diesel cylinder lubricant composition defined above to reduce deposits in a marine diesel cylinder engine running on fuel having at most 1.5% sulphur.
In accordance with the present invention there is also provided use of the marine diesel cylinder lubricant composition defined above to provide lubricity in a marine diesel cylinder engine running on fuel having at most 1.5% sulphur and running at cylinder liner temperatures above 250 C, preferably above 300 C.
Fuels used for diesel engines generally have a high sulphur content, which results in exhaust gases from diesel engines containing large amounts of sulphur oxides (SO,). The sulphur oxides react with moisture also present in the exhaust gases to form sulphuric acid which corrodes the engine. Marine diesel cylinder lubricant compositions therefore include overbased metallic detergents to neutralise the sulphuric acid. Commercial marine diesel cylinder lubricant compositions generally have a total base number ('TBN') of at least 70 (as determined using ASTM D2896).
There is growing environmental pressure to reduce the amount of sulphur in fuels. Therefore, a marine diesel cylinder lubricant composition having a TBN
less than 70 could be used. However, the applicants have found that if a marine diesel cylinder lubricant composition is diluted with base oil to lower the total base number to less than 70, the ability of the lubricant to prevent deposit formation, particularly on the pistons, is significantly reduced.
The aim of the present invention is to provide a marine diesel cylinder lubricant composition having a base number lower than 70 without reducing the ability of the lubricant to prevent deposit formation, particularly on the pistons.
In accordance with the present invention there is provided a marine diesel cylinder lubricant composition for a marine diesel engine running on fuel having a sulphur content of less than 1.5%, the composition having a total base number, as determined according to ASTM D2896, of more than 30 and less than 70, and comprising:
- at least 40 wt% of an oil of lubricating viscosity, and - at least one detergent prepared from at least two surfactants, one of which is a salicylate.
The inventor has found that the marine diesel cylinder lubricant composition defined above is capable of preventing deposit formation, particularly on the pistons, and is also capable of improving resistance to high temperature-induced wear (i.e. scuffing).
The marine diesel cylinder lubricant composition has a total base number (TBN) of less than 70, preferably less than 60, and most preferably less than 50.
Furthermore, the marine diesel cylinder lubricant composition preferably has a total base number (TBN) of more than 32, more preferably more than 35.
In accordance with the present invention there is also provided a method of operating a marine diesel cylinder engine running on fuel having at most 1.5%
sulphur, the method including the step of using the marine diesel cylinder lubricant composition defined above to lubricate the engine.
In accordance with the present invention there is also provided use of the marine diesel cylinder lubricant composition defined above to reduce deposits in a marine diesel cylinder engine running on fuel having at most 1.5% sulphur.
In accordance with the present invention there is also provided use of the marine diesel cylinder lubricant composition defined above to provide lubricity in a marine diesel cylinder engine running on fuel having at most 1.5% sulphur and running at cylinder liner temperatures above 250 C, preferably above 300 C.
Oil of Lubricating Viscosity The oil of lubricating viscosity (sometimes referred to as lubricating oil) may be any oil suitable for the lubrication of a marine engine. The lubricating oil may suitably be an animal, a vegetable or a mineral oil. Suitably the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffinic base or mixed base oil. Alternatively, the lubricating oil may be a synthetic lubricating oil.
Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed. The lubricating oil may generally comprise greater than 60, typically greater than 70, mass % of the composition, and typically have a kinematic viscosity at 100 C
of from 2 to 40, for example for 3 to 15, mm2s 1 and a viscosity index of from 80 to 100, for example from 90 to 95.
Another class of lubricating oils is hydrocracked oils, where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen at high temperatures and moderate pressures. Hydrocracked oils typically have a kinematic viscosity at 1009C of from 2 to 40, for example from 3 to 15, mm2s 1 and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
The oil may include `brightstock' which refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having -a kinematic viscosity at 10020 of from 28 to 36 mm2s 1 and are typically used in a proportion of less than 40, preferably less than 30, more preferably less than 20, mass %, based on the mass of the composition.
Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed. The lubricating oil may generally comprise greater than 60, typically greater than 70, mass % of the composition, and typically have a kinematic viscosity at 100 C
of from 2 to 40, for example for 3 to 15, mm2s 1 and a viscosity index of from 80 to 100, for example from 90 to 95.
Another class of lubricating oils is hydrocracked oils, where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen at high temperatures and moderate pressures. Hydrocracked oils typically have a kinematic viscosity at 1009C of from 2 to 40, for example from 3 to 15, mm2s 1 and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
The oil may include `brightstock' which refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having -a kinematic viscosity at 10020 of from 28 to 36 mm2s 1 and are typically used in a proportion of less than 40, preferably less than 30, more preferably less than 20, mass %, based on the mass of the composition.
The marine diesel cylinder lubricant composition preferably includes at least wt% of oil of lubricating viscosity, more preferably at least 60 wt% of oil of lubricating viscosity.
Comolex/Hybrid Detergent A detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
The detergent comprises a polar head with a long hydrophobic tail. Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
The detergent is a complex/hybrid detergent including at least two surfactants, one of which is a salicylate. The complex detergent preferably includes at least 5 mass% of salicylate, more preferably at least 10 mass% of salicylate. The amount of salicylate in the complex detergent can be determined using techniques such as chromatography, spectroscopy and/or titration, well known to persons skilled in the art. The other surfactant may be a sulphonate, a phenate, a sulphurized phenate, a thiophosphate, a naphthenate, or an oil-soluble carboxylate. The other surfactant is preferably a phenate. The complex detergent preferably includes at least 5 mass% of phenate. The complex detergent may also include at least 5 mass% of sulphonate. The surfactant groups are incorporated during the overbasing process. The metal may be an alkali metal or an alkaline earth metal such as sodium, potassium, lithium, calcium and magnesium. Calcium is preferred.
Comolex/Hybrid Detergent A detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
The detergent comprises a polar head with a long hydrophobic tail. Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
The detergent is a complex/hybrid detergent including at least two surfactants, one of which is a salicylate. The complex detergent preferably includes at least 5 mass% of salicylate, more preferably at least 10 mass% of salicylate. The amount of salicylate in the complex detergent can be determined using techniques such as chromatography, spectroscopy and/or titration, well known to persons skilled in the art. The other surfactant may be a sulphonate, a phenate, a sulphurized phenate, a thiophosphate, a naphthenate, or an oil-soluble carboxylate. The other surfactant is preferably a phenate. The complex detergent preferably includes at least 5 mass% of phenate. The complex detergent may also include at least 5 mass% of sulphonate. The surfactant groups are incorporated during the overbasing process. The metal may be an alkali metal or an alkaline earth metal such as sodium, potassium, lithium, calcium and magnesium. Calcium is preferred.
Examples of complex detergents are described in WO 97/46645 and WO
97/46646.
Preferably, the detergent has a TBN in the range of 250 to 500, more preferably 260 to 450.
Dispersants The marine diesel cylinder lubricant composition may include at least one dispersant. A dispersant is an additive for a lubricating composition whose primary function in cylinder lubricants is to accelerate neutralization of acids by the detergent system.
A noteworthy class of dispersants are "ashless", meaning a non-metallic organic material that forms substantially no ash on combustion, in contrast to metal-containing, hence ash-forming, materials. Ashless dispersants comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g. an 0, P or N atom. The hydrocarbon is an oleophilic group that confers oil-solubility, having for example 40 to 500 carbon atoms. Thus, ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
- Examples of ashless dispersants are succinimides, e.g. polyisobutene succinic anhydride; and polyamine condensation products that may be borated or unborated.
97/46646.
Preferably, the detergent has a TBN in the range of 250 to 500, more preferably 260 to 450.
Dispersants The marine diesel cylinder lubricant composition may include at least one dispersant. A dispersant is an additive for a lubricating composition whose primary function in cylinder lubricants is to accelerate neutralization of acids by the detergent system.
A noteworthy class of dispersants are "ashless", meaning a non-metallic organic material that forms substantially no ash on combustion, in contrast to metal-containing, hence ash-forming, materials. Ashless dispersants comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g. an 0, P or N atom. The hydrocarbon is an oleophilic group that confers oil-solubility, having for example 40 to 500 carbon atoms. Thus, ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
- Examples of ashless dispersants are succinimides, e.g. polyisobutene succinic anhydride; and polyamine condensation products that may be borated or unborated.
Anti-wear Additive The marine diesel cylinder lubricant composition may include at least one anti-wear additive. The anti-wear additive may be metallic or non-metallic, preferably the former.
Dihydrocarbyl dithiophosphate metal salts are examples of the anti-wear additives. The metal in the dihydrocarbyl dithiophosphate metal may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper. Zinc salts are preferred, preferably in the range of 0.1 to 1.5, preferably 0.5 to 1.3, mass %, based upon the total mass of the lubricating oil composition. They may be prepared in accordance with known techniques by firstly forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary. To make the zinc salt, any basic or neutral zinc compound may be used but the oxides, hydroxides and carbonates are most generally employed.
Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
The preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:
[(RO) (R'O) P(S)S]2 Zn where R and R1 may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
Particularly preferred as R and R1 groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, I-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. In order to obtain oil-solubility, the total number of carbon atoms (i.e. in R and R) in the dithiophoshoric acid will generally be 5 or greater. The zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
Anti-oxidants The marine diesel cylinder lubricant composition may include at least one anti-oxidant. The anti-oxidant may be aminic or phenolic. As examples of amines there may be mentioned secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms. As examples of anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
Preferably, the anti-oxidant, if present, is provided in the composition in an amount of up to 3 mass %.
Other additives such as pour point depressants, anti-foamants, and/or demulsifiers may be provided, if necessary.
The terms `oil-soluble' or `oil-dispersable' as used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
Dihydrocarbyl dithiophosphate metal salts are examples of the anti-wear additives. The metal in the dihydrocarbyl dithiophosphate metal may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper. Zinc salts are preferred, preferably in the range of 0.1 to 1.5, preferably 0.5 to 1.3, mass %, based upon the total mass of the lubricating oil composition. They may be prepared in accordance with known techniques by firstly forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary. To make the zinc salt, any basic or neutral zinc compound may be used but the oxides, hydroxides and carbonates are most generally employed.
Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
The preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:
[(RO) (R'O) P(S)S]2 Zn where R and R1 may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
Particularly preferred as R and R1 groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, I-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. In order to obtain oil-solubility, the total number of carbon atoms (i.e. in R and R) in the dithiophoshoric acid will generally be 5 or greater. The zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
Anti-oxidants The marine diesel cylinder lubricant composition may include at least one anti-oxidant. The anti-oxidant may be aminic or phenolic. As examples of amines there may be mentioned secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms. As examples of anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
Preferably, the anti-oxidant, if present, is provided in the composition in an amount of up to 3 mass %.
Other additives such as pour point depressants, anti-foamants, and/or demulsifiers may be provided, if necessary.
The terms `oil-soluble' or `oil-dispersable' as used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
The lubricant compositions of this invention comprise defined individual (i.e.
separate) components that may or may not remain the same chemically before and after mixing.
The present invention is illustrated by, but in no way limited to, the following examples.
Examples A marine diesel cylinder lubricant composition was prepared using a commercial additive package and commercial base oils. The lubricant composition had a total base number of approximately 70 and comprised: an overbased complex calcium detergent having a base number of 410 and including phenate and sulphonate surfactants; a calcium phenate having a base number of 250; a dispersant; and an anti-wear agent. It is noted that this marine diesel cylinder lubricant composition has been approved by marine diesel engine manufacturers because it exhibits good performance in engine field tests. The lubricant was subjected to the Panel Coker Test (details of which are shown below) for piston deposit control testing. The lubricant was then diluted to give a TBN of approximately 40 and also tested using the Panel Coker Test. The test results are shown below in Table 1:
Table 1 Comparative Example 1 Comparative Example 2 Total Base Number 74.1 43.6 Vk 100 18.7 17.0 Panel Coker Test Results Merit Rating 4.34 2.28 Deposits (mg) 34.1 50.7 As shown in Table 1, when the marine diesel cylinder lubricant composition is diluted to give a TBN of approximately 40, the merit rating and the amount of deposits produced are worse.
Example 3 and Comparative Example 4 were then prepared (see Table 2 below) and tested using the Panel Coker Test. Example 3 included a complex detergent having a TBN of 350; the complex detergent included salicylate, phenate and sulphonate surfactants. Example 4 included a complex detergent having a TBN
of 410; the complex detergent included phenate and sulphonate surfactants. It is noted that the complex detergent used in Comparative Example 4 is the same as the complex detergent used in Comparative Example 1.
Table 2 Example 3 Comparative Example 4 Complex detergent 7.15 including salicylate, sulphonate and phenate surfactants Complex detergent 6.10 including sulphonate and phenate surfactants Additive Package 8.60 8.60 comprising a 250 overbased calcium phenate, a borated dispersant, ZDDP and Group I diluent base oil Base Oil, APE 2500 20.00 20.00 available from ExxonMobil Base Oil, APE 600 64.25 65.30 available from ExxonMobil Vk 100 17.2 16.8 BN 42.9 41.0 Panel Coker Test Results Merit Rating 5.06 2.46 Deposits (mg) 28.5 61.6 As shown above in Table 2, Example 3 has a base number of approximately 40 but it still exhibits good results in the Panel Coker Test. Furthermore, the results are better than those produced by Comparative Example 1, which has received 10 approval by the marine diesel engine manufacturers.
Comparative Example 4 shows that if the complex detergent does not include any salicylate, the Panel Coker Test results are poor. Therefore, the complex detergent including phenate and sulphonate as the surfactants is only suitable for use in marine diesel cylinder lubricant compositions having a TBN of at least 70.
The results in Table 2 clearly show that it is possible to formulate a marine diesel cylinder lubricant composition having a base number less than 70 without adversely affecting the amount of deposits produced by the use of a complex detergenf including salicylate as one of the surfactants.
The Panel Coker Test This test involves splashing a lubricating oil composition on to a heated test panel to see if the oil degrades and leaves any deposits that might affect engine performance. The test uses a panel coker tester (model PK-S) supplied by Yoshida Kagaku Kikal Co, Osaka, Japan. The test starts by heating the lubricating oil composition to a temperature of 100 C through an oil bath. A
test panel made of aluminium alloy, which has been cleaned using acetone and heptane and weighed, is placed above the gas engine lubricating oil composition and heated to 320 C using an electric heating element. When both temperatures have stabilised, a splasher splashes the gas engine lubricating oil composition on to the heated test panel in a discontinuous mode: the splasher splashes the oil for 15 seconds and then stops for 45 seconds. The discontinuous splashing takes place over 1 hour, after which the test is stopped, everything is allowed to cool down, and then the aluminium test panel is weighed and rated visually.
The difference in weight of the aluminium test panel before and after the test, expressed in mg, is the weight of deposits. The visual rating is made from 0 to 10, with 0 being for a completely black panel and 10 being for a completely clean panel.
This test is used for simulating the ability of a lubricant composition to prevent deposit formation on pistons. Comparative Example 1 has been approved by marine diesel engine manufacturers. Therefore, its performance in this test is considered to be acceptable. A better lubricant composition would produce a higher merit rating and a lower amount of deposits.
High Temperature HFRR Test The HFRR Test, or High Frequency Reciprocating Rig Test, is a measure of in-use lubricity and the test rig is described in CEC PF 06-T-94 or ISO/TC22/SC7/WG6/N188. In these examples, the friction coefficient is monitored at temperatures up to 350 C. When the friction coefficient reaches a minimum, the temperature is recorded as the temperature of scuffing initiation, i.e. the temperature at which adhesive wear ('scuffing') begins.
separate) components that may or may not remain the same chemically before and after mixing.
The present invention is illustrated by, but in no way limited to, the following examples.
Examples A marine diesel cylinder lubricant composition was prepared using a commercial additive package and commercial base oils. The lubricant composition had a total base number of approximately 70 and comprised: an overbased complex calcium detergent having a base number of 410 and including phenate and sulphonate surfactants; a calcium phenate having a base number of 250; a dispersant; and an anti-wear agent. It is noted that this marine diesel cylinder lubricant composition has been approved by marine diesel engine manufacturers because it exhibits good performance in engine field tests. The lubricant was subjected to the Panel Coker Test (details of which are shown below) for piston deposit control testing. The lubricant was then diluted to give a TBN of approximately 40 and also tested using the Panel Coker Test. The test results are shown below in Table 1:
Table 1 Comparative Example 1 Comparative Example 2 Total Base Number 74.1 43.6 Vk 100 18.7 17.0 Panel Coker Test Results Merit Rating 4.34 2.28 Deposits (mg) 34.1 50.7 As shown in Table 1, when the marine diesel cylinder lubricant composition is diluted to give a TBN of approximately 40, the merit rating and the amount of deposits produced are worse.
Example 3 and Comparative Example 4 were then prepared (see Table 2 below) and tested using the Panel Coker Test. Example 3 included a complex detergent having a TBN of 350; the complex detergent included salicylate, phenate and sulphonate surfactants. Example 4 included a complex detergent having a TBN
of 410; the complex detergent included phenate and sulphonate surfactants. It is noted that the complex detergent used in Comparative Example 4 is the same as the complex detergent used in Comparative Example 1.
Table 2 Example 3 Comparative Example 4 Complex detergent 7.15 including salicylate, sulphonate and phenate surfactants Complex detergent 6.10 including sulphonate and phenate surfactants Additive Package 8.60 8.60 comprising a 250 overbased calcium phenate, a borated dispersant, ZDDP and Group I diluent base oil Base Oil, APE 2500 20.00 20.00 available from ExxonMobil Base Oil, APE 600 64.25 65.30 available from ExxonMobil Vk 100 17.2 16.8 BN 42.9 41.0 Panel Coker Test Results Merit Rating 5.06 2.46 Deposits (mg) 28.5 61.6 As shown above in Table 2, Example 3 has a base number of approximately 40 but it still exhibits good results in the Panel Coker Test. Furthermore, the results are better than those produced by Comparative Example 1, which has received 10 approval by the marine diesel engine manufacturers.
Comparative Example 4 shows that if the complex detergent does not include any salicylate, the Panel Coker Test results are poor. Therefore, the complex detergent including phenate and sulphonate as the surfactants is only suitable for use in marine diesel cylinder lubricant compositions having a TBN of at least 70.
The results in Table 2 clearly show that it is possible to formulate a marine diesel cylinder lubricant composition having a base number less than 70 without adversely affecting the amount of deposits produced by the use of a complex detergenf including salicylate as one of the surfactants.
The Panel Coker Test This test involves splashing a lubricating oil composition on to a heated test panel to see if the oil degrades and leaves any deposits that might affect engine performance. The test uses a panel coker tester (model PK-S) supplied by Yoshida Kagaku Kikal Co, Osaka, Japan. The test starts by heating the lubricating oil composition to a temperature of 100 C through an oil bath. A
test panel made of aluminium alloy, which has been cleaned using acetone and heptane and weighed, is placed above the gas engine lubricating oil composition and heated to 320 C using an electric heating element. When both temperatures have stabilised, a splasher splashes the gas engine lubricating oil composition on to the heated test panel in a discontinuous mode: the splasher splashes the oil for 15 seconds and then stops for 45 seconds. The discontinuous splashing takes place over 1 hour, after which the test is stopped, everything is allowed to cool down, and then the aluminium test panel is weighed and rated visually.
The difference in weight of the aluminium test panel before and after the test, expressed in mg, is the weight of deposits. The visual rating is made from 0 to 10, with 0 being for a completely black panel and 10 being for a completely clean panel.
This test is used for simulating the ability of a lubricant composition to prevent deposit formation on pistons. Comparative Example 1 has been approved by marine diesel engine manufacturers. Therefore, its performance in this test is considered to be acceptable. A better lubricant composition would produce a higher merit rating and a lower amount of deposits.
High Temperature HFRR Test The HFRR Test, or High Frequency Reciprocating Rig Test, is a measure of in-use lubricity and the test rig is described in CEC PF 06-T-94 or ISO/TC22/SC7/WG6/N188. In these examples, the friction coefficient is monitored at temperatures up to 350 C. When the friction coefficient reaches a minimum, the temperature is recorded as the temperature of scuffing initiation, i.e. the temperature at which adhesive wear ('scuffing') begins.
This test is used for assessing the ability of a lubricant composition to control adhesive wear in large bore crosshead engines. The result given for Comparative Example 1 is considered to be acceptable by manufacturers of marine diesel engines. A better lubricant composition would produce a higher temperature of scuffing initiation.
Example 3 and Comparative Examples 1 and 2 were tested using the HFRR test.
The test results are shown below:
Table 3 Example 3 Comparative Comparative Example 1 Example 2 Temperature of 338 270 277 Scuffing Initiation (degrees C) As shown above, Example 3 provides `scuff-free' lubrication up to 338 C, whereas Comparative Examples 1 and 2 only provide `scuff-free' lubrication up to 270 C and 277 C respectively. These results show that marine diesel cylinder lubricant compositions of the present invention having a total base number below 70 can provide lubrication at higher temperatures than commercially available lubricant compositions having total base numbers of at least 70.
Example 3 and Comparative Examples 1 and 2 were tested using the HFRR test.
The test results are shown below:
Table 3 Example 3 Comparative Comparative Example 1 Example 2 Temperature of 338 270 277 Scuffing Initiation (degrees C) As shown above, Example 3 provides `scuff-free' lubrication up to 338 C, whereas Comparative Examples 1 and 2 only provide `scuff-free' lubrication up to 270 C and 277 C respectively. These results show that marine diesel cylinder lubricant compositions of the present invention having a total base number below 70 can provide lubrication at higher temperatures than commercially available lubricant compositions having total base numbers of at least 70.
Claims (14)
1. A marine diesel cylinder lubricant composition for a marine diesel engine running on fuel having a sulphur content of less than 1.5% by mass, the composition having a total base number, as determined according to ASTM D2896, of more than 30 and less than 70, and comprising:
- at least 40 wt% of an oil of lubricating viscosity, and - at least one detergent prepared from at least two surfactants, one of which is a salicylate.
- at least 40 wt% of an oil of lubricating viscosity, and - at least one detergent prepared from at least two surfactants, one of which is a salicylate.
2. The marine diesel cylinder lubricant composition as claimed in claim 1, wherein the detergent includes at least 5 mass% of salicylate.
3. The marine diesel cylinder lubricant composition as claimed in claim 1, wherein the detergent includes at least 10 mass% of salicylate.
4. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 3, wherein the detergent further includes at least 5 mass% of phenate and optionally at least 5 mass% of sulphonate.
5. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 4, wherein the lubricant has a base number of less than 60.
6. The marine diesel cylinder lubricant composition as claimed in claim 5, wherein the lubricant has a base number of less than 50.
7. The marine diesel cylinder lubricant composition as claimed in claim 5, wherein the lubricant has a base number of between 32 and 60.
8. The marine diesel cylinder lubricant composition as claimed in claim 5, wherein the lubricant has a base number of between 32 and 50.
9. The marine diesel cylinder lubricant composition as claimed in claim 5, wherein the lubricant has a base number of between 35 and 50.
10. The marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 9, further including at least one of the following: a dispersant, an anti-wear agent, an anti-oxidant, a pour point depressant, an anti-foamant and a demulsifier.
11. A method of operating a marine diesel engine running on fuel having at most 1.5% by mass of sulphur, the method including the step of using the marine diesel cylinder lubricant composition claimed in any one of claims 1 to 5 to lubricate the engine.
12. Use of the marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 5 to reduce deposits in a marine diesel engine running on fuel having at most 1.5% by mass of sulphur.
13. Use of the marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 5 to provide lubricity in a marine diesel engine running on fuel having at most 1.5% by mass of sulphur and running at temperatures above 250°C.
14. Use of the marine diesel cylinder lubricant composition as claimed in any one of claims 1 to 5 to provide lubricity in a marine diesel engine running on fuel having at most 1.5% by mass of sulphur and running at temperatures above 300°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03253769 | 2003-06-13 | ||
| EP03253769.8 | 2003-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2471202A1 CA2471202A1 (en) | 2004-12-13 |
| CA2471202C true CA2471202C (en) | 2011-11-01 |
Family
ID=33547787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2471202A Expired - Fee Related CA2471202C (en) | 2003-06-13 | 2004-06-11 | Marine diesel cylinder lubricant composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20050003972A1 (en) |
| JP (1) | JP4928070B2 (en) |
| CN (1) | CN100500816C (en) |
| AU (1) | AU2004202588B2 (en) |
| CA (1) | CA2471202C (en) |
| SG (1) | SG126767A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1721955B1 (en) * | 2005-05-11 | 2011-08-03 | Infineum International Limited | Fuel compositions |
| EP1728849B1 (en) * | 2005-05-27 | 2019-12-18 | Infineum International Limited | A method of lubricating the cylinder liner and the crankcase of a cross-head marine diesel engine |
| US8076274B2 (en) * | 2006-07-20 | 2011-12-13 | Infineum International Limited | Lubricating oil composition |
| EP2132287A1 (en) * | 2007-03-30 | 2009-12-16 | BP p.l.c. | Lubrication methods |
| EP2003189A1 (en) * | 2007-06-12 | 2008-12-17 | BP p.l.c. | Lubrication methods |
| EP2507347A1 (en) * | 2009-11-30 | 2012-10-10 | The Lubrizol Corporation | Methods of controlling sulfur trioxide levels in internal combustion engines |
| EP2719751B1 (en) * | 2012-06-07 | 2021-03-31 | Infineum International Limited | Marine engine lubrication |
| US9434906B2 (en) * | 2013-03-25 | 2016-09-06 | Chevron Oronite Company, Llc | Marine diesel engine lubricating oil compositions |
| KR102274235B1 (en) | 2013-11-06 | 2021-07-09 | 셰브런 오로나이트 테크놀로지 비.브이. | Marine diesel cylinder lubricant oil compositions |
| JP6509240B2 (en) | 2013-11-06 | 2019-05-08 | シェブロン・オロナイト・テクノロジー・ビー．ブイ． | Marine diesel cylinder lubricating oil composition |
| CN107001977B (en) * | 2014-11-18 | 2021-02-05 | Jxtg能源株式会社 | Cylinder lubricating oil composition for crosshead diesel engine equipped with scrubber |
| JP6297477B2 (en) * | 2014-11-18 | 2018-03-20 | Ｊｘｔｇエネルギー株式会社 | Cylinder lubricating oil composition for crosshead type diesel engine mounted on scrubber |
| JP6386348B2 (en) * | 2014-11-18 | 2018-09-05 | Ｊｘｔｇエネルギー株式会社 | Cylinder lubricating oil composition for crosshead type diesel engine mounted on scrubber |
| KR20160092963A (en) * | 2016-07-13 | 2016-08-05 | 윤종식 | Method of preventing traffic accidents in crossroad for signal violation and overspeed, and system of the same |
| US10603075B1 (en) | 2018-11-30 | 2020-03-31 | Ohana Biosciences, Inc. | Compositions and methods for enhancing sperm function |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9611318D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| GB9611428D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| GB9611424D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
| GB9709006D0 (en) * | 1997-05-02 | 1997-06-25 | Exxon Chemical Patents Inc | Lubricating oil compositions |
| CA2283105C (en) * | 1997-11-28 | 2008-10-07 | Infineum Usa L.P. | Lubricating oil compositions |
| GB9800436D0 (en) * | 1998-01-09 | 1998-03-04 | Exxon Chemical Patents Inc | Marine lubricant compositions |
| US6277794B1 (en) * | 1998-12-28 | 2001-08-21 | Infineum Usa L.P. | Lubricant compositions |
| GB9908771D0 (en) * | 1999-04-17 | 1999-06-09 | Infineum Uk Ltd | Lubricity oil composition |
| ATE491775T1 (en) * | 1999-09-13 | 2011-01-15 | Infineum Int Ltd | A METHOD OF LUBRICATION FOR TWO-STROKE MARINE DIESEL ENGINES |
| JP4011815B2 (en) * | 2000-02-14 | 2007-11-21 | シェブロンジャパン株式会社 | Lubricating oil composition for two-cycle crosshead diesel internal combustion engine and additive composition for lubricating oil composition |
| GB0011115D0 (en) * | 2000-05-09 | 2000-06-28 | Infineum Int Ltd | Lubricating oil compositions |
| EP1209218A1 (en) * | 2000-11-27 | 2002-05-29 | Infineum International Limited | Lubricating oil compositions |
| EP1229101A1 (en) * | 2001-02-06 | 2002-08-07 | Infineum International Limited | Marine diesel engine lubricant |
| EP1229102A1 (en) * | 2001-02-06 | 2002-08-07 | Infineum International LTD | Lubricating oil composition |
| EP1236792B1 (en) * | 2001-02-16 | 2007-01-03 | Infineum International LTD | Use of overbased detergent additives to suspend asphaltene compounds |
| EP1236791A1 (en) * | 2001-02-16 | 2002-09-04 | Infineum International Limited | Overbased detergent additives |
| US6884531B2 (en) * | 2001-05-21 | 2005-04-26 | Saudi Arabian Oil Company | Liquid hydrocarbon based fuels for fuel cell on-board reformers |
-
2004
- 2004-06-08 US US10/863,041 patent/US20050003972A1/en not_active Abandoned
- 2004-06-11 AU AU2004202588A patent/AU2004202588B2/en not_active Ceased
- 2004-06-11 CN CNB2004100481099A patent/CN100500816C/en not_active Expired - Fee Related
- 2004-06-11 SG SG200404073A patent/SG126767A1/en unknown
- 2004-06-11 CA CA2471202A patent/CA2471202C/en not_active Expired - Fee Related
- 2004-06-11 JP JP2004173663A patent/JP4928070B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU2004202588A1 (en) | 2005-01-06 |
| CN1572864A (en) | 2005-02-02 |
| AU2004202588B2 (en) | 2009-05-21 |
| US20050003972A1 (en) | 2005-01-06 |
| SG126767A1 (en) | 2006-11-29 |
| CN100500816C (en) | 2009-06-17 |
| JP2005002341A (en) | 2005-01-06 |
| CA2471202A1 (en) | 2004-12-13 |
| JP4928070B2 (en) | 2012-05-09 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20180611 |