EP1298190B1 - Compositions lubrifiantes pour la lubrification d'un moteur diesel marin - Google Patents
Compositions lubrifiantes pour la lubrification d'un moteur diesel marin Download PDFInfo
- Publication number
- EP1298190B1 EP1298190B1 EP02078107A EP02078107A EP1298190B1 EP 1298190 B1 EP1298190 B1 EP 1298190B1 EP 02078107 A EP02078107 A EP 02078107A EP 02078107 A EP02078107 A EP 02078107A EP 1298190 B1 EP1298190 B1 EP 1298190B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- composition
- lubricating oil
- oil composition
- lubricating
- 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 - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 100
- 239000010687 lubricating oil Substances 0.000 title claims description 58
- 239000003599 detergent Substances 0.000 claims description 44
- 239000000654 additive Substances 0.000 claims description 43
- 239000003921 oil Substances 0.000 claims description 35
- 239000002270 dispersing agent Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000005078 molybdenum compound Substances 0.000 claims description 24
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 23
- 239000010763 heavy fuel oil Substances 0.000 claims description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 230000001050 lubricating effect Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 235000019198 oils Nutrition 0.000 description 31
- -1 tri-decyl adipate Chemical compound 0.000 description 27
- 239000003446 ligand Substances 0.000 description 19
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000314 lubricant Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000002199 base oil Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 239000010727 cylinder oil Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 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
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003873 salicylate salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010689 synthetic lubricating oil Substances 0.000 description 2
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910017489 Cu I Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910015463 Mo3S4 Inorganic materials 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000003819 basic metal compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- KGGZTXSNARMULX-UHFFFAOYSA-L copper;dicarbamodithioate Chemical class [Cu+2].NC([S-])=S.NC([S-])=S KGGZTXSNARMULX-UHFFFAOYSA-L 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- JLYVRXJEQTZZBE-UHFFFAOYSA-N ctk1c6083 Chemical compound NP(N)(N)=S JLYVRXJEQTZZBE-UHFFFAOYSA-N 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- 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
- C10M2215/28—Amides; Imides
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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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
- 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
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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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/09—Complexes with metals
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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
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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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
- C10N2030/02—Pour-point; Viscosity index
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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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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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
- C10N2030/52—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
Definitions
- the present invention concerns improved lubricating oil compositions for residual fuel oil-fuelled diesel engines.
- the present invention concerns lubricating oil compositions that demonstrate improved cylinder liner wear performance.
- the cylinders are lubricated separately from the other engine components.
- the cylinders are lubricated on a total loss basis with the cylinder oil being injected separately to quills on each cylinder by means of lubricators positioned around the cylinder liner. Oil is distributed to the lubricators by means of pumps, which are, in modern engine designs, actuated to apply the oil directly onto the rings to reduce wastage of the oil.
- the high stresses encountered in these engines and the use of residual fuels creates the need for lubricants with a high detergency and neutralising capability even though the oils are exposed to thermal and other stresses only for short periods of time.
- Residual fuels commonly used in these diesel engines typically contain significant quantities of sulfur, which, in the combustion process, combine with water to form sulfuric acid, the presence of which leads to corrosive wear.
- sulfuric acid the presence of which leads to corrosive wear.
- areas around the cylinder liners and piston rings can be corroded and worn by the acid. Therefore, it is important for diesel engine lubricating oils to have the ability to resist such corrosion and wear.
- US-A-4842755 discloses the use of borated dispersants and zinc dialkyldithiophosphates in a marine cylinder lubricating oil composition to provide anti-wear performance in the cylinder liner and piston ring areas.
- US-A-4948522 discloses marine diesel cylinder lubricants comprising a borated dispersant and a polybutene, and optionally a zinc dialkyldithiophosphate and/or an overbased metal detergent.
- the lubricants have improved ring wear and linear wear performance and good protection against corrosion.
- US-A-6140280 discloses succinimide compounds that exhibit corrosion resistance and wear resistance in diesel engines. It also discloses that conventional anti-wear agents, such as zinc dithiophosphates and molybdenum dithiocarbamates, may be used as co-additives.
- WO 99/64543 discloses cylinder oils of defined characteristics and a liquid polyisobutylene.
- the cylinder oils provide improved performance including protection against corrosive, friction and abrasive wear.
- the aim of the present invention is to provide a lubricating oil composition that offers effective cylinder liner protection, particularly in the areas of the cylinder that are prone to corrosive wear.
- the present invention provides a lubricating oil composition for a residual fuel oil-fuelled diesel engine for marine and stationary applications, comprising:
- the present invention provides use of the lubricating oil composition in a cylinder of a two-stroke cross-head marine diesel engine, wherein the cylinder is characterised by a power output of 4000 or greater, such as 4200 or greater, preferably 4500 or greater, more preferably in the range of 4500 to 6000, kW.
- the present invention provides the use of an oil-soluble or oil-dispersible trinuclear molybdenum compound or a composition, such as an oleaginous composition, comprising the trinuclear molybdenum compound, to reduce corrosive wear in a cylinder liner of a residual fuel oil-fuelled diesel engine, preferably a cross-head marine engine.
- the present invention provides a method of reducing corrosive wear in a cylinder liner of a residual fuel oil-fuelled diesel engine, preferably a cross-head marine, comprising supplying to the walls of the cylinder a lubricating oil composition of the first aspect.
- the present invention provides an additive composition comprising:
- Diesel fuel oils can in general be divided into two main categories - distillates and heavy or residual fuels. Distillates consist of one or more distillate fractions.
- Heavy or residual fuels are fuels that comprise at least a proportion of a residual oil, i.e. oil that remains after the distilled fractions have been removed from unrefined oil.
- the composition of the residual fuel will vary with the composition of the starting oil, usually a crude oil, and will also vary depending upon the distillation conditions. However, by its nature, residual fuel oil is of high molecular weight, contains significant quantities of sulfur and has a high boiling point.
- residual oil is understood by those skilled in the art; it is defined according to the standards ISO 8217, ISO RME25 and ISO RME35.
- the present invention is suitable for large residual fuel oil-fuelled diesel engines, such as diesel engines of the cross-head type used in marine and heavy stationary applications, and of the trunk piston type found in marine applications.
- Large diesel engines are mainly employed for marine propulsion and power generation.
- Diesel engines suitable in the present invention can also be fuelled by a mixture of distillate and residual fuels.
- Cross-head engines tend to be two-stroke, whereas trunk piston engines tend to be four-stroke.
- Four-stroke trunk piston engines may have a speed of 100 to 2,000, preferably 300 to 1,800, more preferably 350 to 1500, rpm, and the cylinder is characterised by power output of 50 to 10000, preferably 100 to 6000, more preferably 150 to 5000, kW.
- Two-stroke cross-head engines may have a speed of 40 to 600, preferably 60 to 500, such as 80 to 300, rpm and the cylinder is characterised by a power output of 4000 or greater, such as 4200 or greater, preferably 4500 or greater, more preferably in the range of 4500 to 6000, kW.
- the engines may, for example, have from 6 to 12 cylinders and their total output may, for example, be in the range of 18,000 to 70,000 kW.
- the bore of the cylinder may, for example, be 850 or greater, such as 900 or greater, preferably in the range of 900 to 1000, cm.
- lubricating oil compositions of the present invention are particularly useful in cross-head engines, such as two-stroke cross-head engines for marine propulsion and stationary power generation.
- the total base number (TBN) of the lubricating oil composition is preferably 30 to 95, more preferably 40 to 90, even more preferably 65 to 90.
- the viscosity at 100 °C of the lubricating oil composition is preferably 9 to 25, more preferably 12 to 25, even more preferably 16 to 25, such as 18 to 22, mm 2 s -1 .
- the viscosity index, as defined by ASTM D2270, of the lubricating oil composition is preferably at least 90, more preferably at least 95, especially at least 100, for example in the range from 90 to 110.
- Lubricating oil compositions used in large residual-fuelled diesel engines can become contaminated with residual fuel during use, particularly in four-stroke trunk piston engines. Therefore, the lubricating oil compositions of the invention can also contain a residual fuel oil.
- lubricating oil compositions of the present invention will typically be monograde, i.e. compositions that exhibit little or no viscosity index improvement properties, for example, an SAE30, SAE 40, SAE 50 or higher lubricant.
- lubricating oil compositions of the present invention preferably do not comprise a viscosity index modifier.
- the oil of lubricating viscosity may be any oil suitable for the lubrication of a large diesel engine, such as a cross-head engine or a trunk piston engine.
- the lubricating oil may suitably be an animal, a vegetable or a mineral oil.
- the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffinic base or mixed base oil.
- 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 tri-decyl adipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed.
- hydrocracked oils 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 kinematic viscosity at 100 °C of from 2 to 40, for example from 3 to 15, mm 2 s -1 and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
- 'brightstock' refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum, which generally have a kinematic viscosity at 100 °C of from 28 to 36 mm 2 s -1 and are typically used in a proportion of less than 30, preferably less than 20, more preferably less than 15, most preferably less than 10, such as less than 5, mass %, based on the mass of the lubricating oil composition.
- the lubricating oil compositions comprise an oil-soluble or oil-dispersible trinuclear molybdenum compound.
- the trinuclear (or trimeric) molybdenum compounds are especially those of the formula Mo 3 S k L n Q z and mixtures thereof, wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble in the oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
- the ligands may be selected from the group consisting of -X-R and mixtures thereof, wherein X, X 1 , X 2 , and Y are selected from the group consisting of oxygen and sulfur, and wherein R 1 , R 2 , and R are selected from hydrogen and organo groups that may be the same or different.
- the organo groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group.
- hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character.
- substituents include the following:
- the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble in the oil.
- the number of carbon atoms in each group will generally range between 1 to 100, preferably from 1 to 30, and more preferably between 4 to 20.
- Preferred ligands include dialkyldithiophosphate, alkylxanthate, carboxylates, dialkyldithiocarbamate (“dtc”), and mixtures thereof. Most preferred are the dialkyldithiocarbamates.
- Oil-soluble trinuclear molybdenum compounds can be prepared by reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide.
- a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values
- oil-soluble trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur-abstracting agent such as cyanide ions, sulfite ions, or substituted phosphines.
- a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O)
- a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate
- sulfur-abstracting agent such as cyanide ions, sulfite ions, or substituted phosphines.
- a trinuclear molybdenum-sulfur halide salt such as [M'] 2 [Mo 3 S 7 A 6 ], where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble trinuclear molybdenum compound.
- the appropriate liquid/solvent may be, for example, aqueous or organic.
- the ligand chosen must have a sufficient number of carbon atoms to render the compound soluble in the lubricating composition.
- Trinuclear molybdenum compounds for use in the compositions of this invention can be those of the formula Mo 3 S 7 ((alkyl) 2 dtc) 4 where the alkyl has about 8 to 18 carbon atoms.
- the alkyl is preferably a "coco" alkyl chain which is a mixture of chains of varying even numbers of carbon atoms from typically a C 8 to C 18 alkyl, mainly C 10 , C 12 and C 14 alkyls derived from coconut oil.
- trinuclear molybdenum compounds include a sulfurized trinuclear molybdenum containing composition prepared by (i) reacting an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a phosphoramide, a thiophosphoramide, a Mannich base, a dispersant viscosity index improver, or a mixture thereof, in the presence of a polar promoter, to form a trinuclear molybdenum complex, and (ii) reacting the trinuclear molybdenum complex with a sulfur-containing compound, to thereby form a sulfur- and molybdenum-containing composition.
- a basic nitrogen compound selected from the group consisting of succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a phosphoramide, a thiophosphoramide, a Mannich base,
- the trinuclear molybdenum compound is preferably fully sulfurised, i.e. the core contains only sulfur, for example Mo 3 S 4 and Mo 3 S 7 .
- the trinuclear molybdenum compound is preferably a dithiocarbamate compound, such a trinuclear molybdenum dithiocarbamate; especially effective compounds are molybdenum dialkyldithiocarbamate compounds represented by the formula Mo 3 S 7 ((alkyl) 2 dtc) 4 .
- the lubricating oil composition preferably contains 1 to 10000, more preferably 5 to 5000, even more preferably 10 to 1000, especially 50 to 750, ppm of molybdenum by mass, based on the mass of the oil composition.
- Oil-soluble or oil-dispersible molybdenum compounds such as trinuclear molybdenum dithiocarbamates, have been found to be particularly effective in preventing corrosive wear in the cylinder liner.
- the amount of molybdenum is measured according to ASTM D5185.
- the lubricating oil compositions can also comprise a dispersant.
- Dispersants maintain oil-insoluble substances, resulting from oxidation during use, in suspension in the fluid, thus preventing sludge flocculation and precipitation or deposition on metal parts.
- ashless dispersants are organic materials, which form substantially no ash on combustion, in contrast to metal-containing (and thus ash-forming) detergents. Borated metal-free dispersants are regarded herein as ashless dispersants.
- the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
- the dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono- and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannick condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine, and Koch reaction products.
- the polymer backbone is typically an olefin polymer, especially polymers comprising a major molar amount (i.e. greater than 50 mole %) of a C 2 to C 18 olefin (e.g., ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene), and typically a C 2 to C 5 olefin.
- a C 2 to C 18 olefin e.g., ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene
- the oil-soluble polymeric hydrocarbon backbone may be a homopolymer (e.g., polypropylene or polyisobutylene) or a copolymer of two or more of such olefins (e.g., copolymers of ethylene and an alpha-olefin such as propylene and butylene or copolymers of two different alphaolefins).
- a homopolymer e.g., polypropylene or polyisobutylene
- a copolymer of two or more of such olefins e.g., copolymers of ethylene and an alpha-olefin such as propylene and butylene or copolymers of two different alphaolefins.
- olefin polymers polybutenes and specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
- PIB polyisobutenes
- poly-n-butenes such as may be prepared by polymerization of a C 4 refinery stream.
- Another preferred class of olefin polymers is ethylene alpha-olefin (EAO) copolymers or alpha-olefin homo- and copolymers such as may be prepared using metallocene chemistry having in each case a high degree (e.g. >30%) of terminal vinylidene unsaturation.
- EAO ethylene alpha-olefin
- the polymer backbone will usually have number average molecular weight ( M n) within the range of from 100 to 20,000 or 10,000.
- M n of the backbone is preferably within the range of 250 or 500 to 10,000, more preferably 700 to 5,000.
- Both relatively low molecular weight ( M n 500 to 1500) and relatively high molecular weight ( M n 1500 to 5,000 or greater) polymers are useful to make dispersants.
- Particularly useful olefin polymers for use in dispersants have M n within the range of from 900 to 3000.
- the olefin polymers used to prepare dispersants preferably have approximately one terminal double bond per polymer chain.
- Suitable dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids in which the hydrocarbon groups contain 50 to 400 carbon atoms, examples of such derivatives being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
- Such hydrocarbyl-substituted carboxylic acids may be reacted with, for example, a nitrogen-containing compound, advantageously a polyalkylene polyamine, or with an ester.
- Particularly preferred dispersants are the reaction products of polyalkylene amines with alkenyl succinic anhydrides.
- the dispersant can be further post-treated by a variety of conventional post treatments such as boration, as generally described in US 3,087,936 and 3,254,025.
- This is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from the group consisting of boron oxide, boron halides, boron acids and esters of boron acids or highly borated low M w dispersant, in an amount to provide a boron to nitrogen mole ratio of 0.01 - 5.0.
- the dispersants contain from 0.05 to 2.0, e.g. 0.05 to 1.5 or 0.9, mass % of boron based on the total mass (active ingredient basis) of the borated acyl nitrogen compound.
- Preferred for use in the invention is a polyisobutenyl succinimide dispersant wherein the M n of the polyisobutenyl groups is from 750 to 3000, such as 900 to 1200 or 2000 to 2300.
- the amount of dispersant, based on nitrogen derived from the dispersant, in the lubricating oil composition is preferably up to 1.0, more preferably 0.001 to 0.08, such as 0.005 to 0.55 or 0.50, mass %, based on the mass of the lubricating oil composition.
- the amount of dispersant, based on boron derived from the dispersant, in the lubricating oil composition is preferably not more than 0.5, such as not more than 0.25, for example 0.005 to 0.1, mass %, based on the mass of the lubricating oil composition.
- the dispersant is a borated dispersant, such as a borated succinimide.
- the amount of boron is measured according to ASTM D5185; the amount of nitrogen is measured according to ASTM D5291; the M n can be determined by several known techniques - a convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information.
- GPC gel permeation chromatography
- the lubricating oil composition comprises a detergent composition, which comprises one or more overbased detergents.
- 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.
- a metal base can be 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.
- a metal compound such as an oxide or hydroxide
- an acidic gas such as carbon dioxide
- the metals can be selected from Group 1 and Group 2 metals, e.g., sodium, potassium, lithium, calcium, and magnesium. Calcium and magnesium are preferred; more preferably the metal is calcium.
- Surfactants that may be used include organic carboxylates, for example, aliphatic carboxylates and aromatic carboxylates, such as salicylates, non-sulfurised or sulfurised; sulfonates; phenates, non-sulfurised or sulfurised; thiophosphonates; and naphthenates.
- organic carboxylates for example, aliphatic carboxylates and aromatic carboxylates, such as salicylates, non-sulfurised or sulfurised; sulfonates; phenates, non-sulfurised or sulfurised; thiophosphonates; and naphthenates.
- Suitable detergents include overbased metal phenates, metal sulfonates, metal salicylates and metal carboxylates, where the metal is selected from sodium, calcium and magnesium; preferably the metal is calcium.
- a detergent in the form of a hybrid complex detergent wherein the basic material is stabilised by more than one type of surfactant (see WO 97/46643, WO 97/46644, WO 97/46646, and WO 97/46647).
- a single type of organic acid may contain a mixture of organic acids of the same type.
- a sulphonic acid may contain a mixture of sulphonic acids of varying molecular weights.
- Such an organic acid composition is considered as one type.
- complex detergents are distinguished from mixtures of two or more separate overbased detergents, an example of such a mixture being one of an overbased salicylate detergent with an overbased phenate detergent.
- EP-A-0 750 659 describes a calcium salicylate phenate complex made by carboxylating a calcium phenate and then sulfurising and overbasing the mixture of calcium salicylate and calcium phenate. Such complexes may be referred to as "phenalates"
- Surfactants for the surfactant system of the overbased metal detergent may contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
- hydrocarbyl groups in surfactants for use in accordance with the invention are aliphatic groups, preferably alkyl or alkylene groups, especially alkyl groups, which may be linear or branched. The total number of carbon atoms in the surfactants should be at least sufficient to impact the desired oil-solubility.
- the proportion of one detergent type (e.g. calcium sulfonate) to another detergent type (e.g. sodium phenate) in the detergent composition is not critical.
- the proportion of one surfactant to another in a complex detergent is not critical.
- the detergent composition may comprise a major proportion of a phenate detergent or comprises a complex hybrid detergent having a major proportion of a phenate surfactant, where the phenate detergent or the complex hybrid detergent is preferably a calcium salt.
- the overbased detergents of the present invention may have a TBN of at least 200, preferably at least 250, especially at least 300, such as up to 600.
- the lubricating oil compositions of the present invention have a sufficient amount of additives, for example, detergents, whether neutral or overbased, to provide the required TBN.
- the detergent composition may be used up to 30, preferably 2 to 15 or to 20, mass % of detergent composition, based on the mass of the lubricating oil composition.
- the lubricants may include an antiwear agent as a co-additive and may also contain other co-additives, for example, antioxidants, antifoaming agents and/or rust inhibitors. Further details of particular co-additives are as follows.
- Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service, evidence of such deterioration being, for example, the production of varnish-like deposits on metal surfaces and of sludge, and viscosity increase.
- Suitable oxidation inhibitors include sulphurized alkyl phenols and alkali or alkaline earth metal salts thereof; diphenylamines; phenyl-naphthylamines; and phosphosulphurized or sulphurized hydrocarbons.
- oxidation inhibitors or antioxidants that may be used in the lubricant comprise oil-soluble copper compounds.
- the copper may be blended therein as any suitable oil-soluble copper compound.
- oil-soluble is meant that the compound is oil-soluble under normal blending conditions in the base stock or an additive package.
- the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio-phosphate.
- the copper may be added as the copper salt of a synthetic or natural carboxylic acid, for example, a C8 to C18 fatty acid, an unsaturated acid, or a branched carboxylic acid.
- oil-soluble copper dithiocarbamates, sulphonates, phenates, and acetylacetonates are basic, neutral or acidic copper Cu I and/or Cu II salts derived from alkenyl succinic acids or anhydrides.
- Additional detergents and metal rust inhibitors include the metal salts, which may be overbased and have a TBN less than 300, of sulphonic acids, alkyl phenols, sulphurized alkyl phenols, alkyl salicylic acids, thiophosphonic acids, naphthenic acids, and other oil-soluble mono- and dicarboxylic acids.
- the TBN of the metal salts may be less than 200.
- Zinc dihydrocarbyl dithiophosphates are very widely used as antiwear agents.
- ZDDPs are those of the formula Zn[SP(S)(OR 1 )(OR 2 )] 2 wherein R 1 and R 2 represent hydrocarbyl groups such as alkyl groups that contain from 1 to 18, preferably 2 to 12, carbon atoms.
- R 1 and R 2 represent hydrocarbyl groups such as alkyl groups that contain from 1 to 18, preferably 2 to 12, carbon atoms.
- ashless or non-metal containing additives such as sulfur and/or phosphorus containing compounds, for example, sulfurised phenol and amine dithiophosphate.
- the oil compositions of the present invention may contain 0 to 0.2, preferably 0.05 to 0.15, more preferably 0.01 to 0.1, mass % of phosphorus, based on the mass of the oil composition.
- the oil composition contains less than 150, preferably less than 100, more preferably less than 50, for example 0, ppm of phosphorus.
- Foam control may be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
- Typical proportions for additives for a four-stroke trunk piston engine oil composition are as follows: Additive Mass % a.i. (Broad) Mass % a.i. (Preferred) Detergent(s) 0.5-10 2-7 Dispersant(s) 0.5-5 1-3 Anti-wear agent(s) 0.1-1.5 0.5-1.3 Oxidation inhibitor 0.2-2 0.5-1.5 Rust inhibitor 0.03-0.15 0.05-0.1 Pour point depressant 0.03-0.15 0.05-0.1 Mineral or synthetic base oil Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance
- Typical proportions for additives for a two-stroke cross-head oil composition are as follows: Additive Mass % a.i.* (Broad) Mass % a.i. (Preferred) Detergent(s) 1-18 3-12 Dispersant(s) 0.5-5 1-3 Anti-wear agent(s) 0.1-1.5 0.5-1.3 Pour point depressant 0.03-0.15 0.05-0.1 Mineral or synthetic base oil Balance Balance
- additives When a plurality of additives is employed it may be desirable, although not essential, to prepare one or more additive compositions (also known as packages) or concentrates comprising the additives, whereby several additives can be added simultaneously to the oil of lubricating viscosity to form the lubricant or lubricating oil composition. Dissolution of the additive package(s) into the oil of lubricating viscosity may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
- the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function, in the final lubricant when the additive package(s) is/are combined with a predetermined amount of oil of lubricating viscosity.
- the molybdenum compound in accordance with the present invention may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90 and preferably from 5 to 75 and most preferably from 8 to 60, mass %, the remainder being base oil or other compatible solvents.
- the lubricating oil composition may typically contain 5 to 40, preferably 10 to 38, more preferably 16 to 34, mass % of the additive package(s), based on active ingredient.
- Lubricating oil compositions were prepared by methods known in the art. Table 1 shows the compositional details of Example 1 and Comparative Examples 1 and 2. Example 1 and Comparative Examples 1 & 2 were blended so that the resulting lubricating oil composition has a TBN of 70 and viscosity at 100°C of about 20 mm 2 s -1 .
- Example 1 an example according to the present invention, is a lubricating oil composition comprising 550 ppm of molybdenum; Comparative Examples 1 and 2 contain the same detergents and dispersant as Example 1, but Comparative Example 1 contains a zinc dithiophosphate additive instead of the molybdenum compound and Comparative Example 2 does not contain the molybdenum compound or the zinc compound.
- Comparative Example 3 is a commercial lubricating oil composition having a TBN of 70 and viscosity at 100°C of about 20 mm 2 s -1 .
- Example 1 and Comparative Examples 1 to 3 were tested for cylinder liner wear performance in a slow speed two-stroke cross-head "Bolnes" engine.
- Such engines are widely used by those skilled in the art for lubricating performance evaluation such as disclosed in a presentation by Nippon Mitsubishi Oil Company on 10 May 2001 at CIMAC conference entitled "The influence of the neutralisation ability of marine lubricants on engine lubrication" Takeshmia et al.
- Example 1 provides better wear protection than any one of Comparative Examples 1 to 3, in particular better than Comparative Example 1, which contains ZDDP. This improvement is especially evident in positions 2 to 5 of the cylinder.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Claims (9)
- Composition d'huile lubrifiante pour un moteur Diesel alimenté en huile combustible résiduelle pour des applications marines et fixes, comprenant :(a) une huile ayant une viscosité lubrifiante en une quantité principale ;(b) un composé trinucléaire du molybdène soluble dans l'huile ou dispersable dans l'huile en une petite quantité ; et(c) une composition de détergent comprenant un ou plusieurs détergents à base de métaux surbasifiés ;
- Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, sous la forme d'une composition d'huile lubrifiante pour un moteur Diesel marin 'à crosse alimenté en huile combustible résiduelle, ayant une valeur de TBN de 30 à 95 et une viscosité à 100°C dans la plage de 9 à 25, par exemple de 12 à 25 mm2s-1.
- Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, comprenant en outre :(d) un dispersant qui a un squelette d'hydrocarbure ayant un poids moléculaire de 100 à 10 000.
- Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, dans laquelle le composé du molybdène est présent en une quantité de 1 à 10 000 ppm en poids de molybdène par rapport au poids de la composition d'huile.
- Composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, comprenant en outre une huile combustible résiduelle.
- Utilisation de la composition d'huile lubrifiante selon l'une quelconque des revendications précédentes dans un moteur Diesel marin à crosse à deux temps dans lequel le cylindre est caractérisé par une puissance utile de 4000 ou plus, par exemple de 4200 ou plus, de préférence de 4500 ou plus, de façon plus préférée dans la plage de 4500 à 6000 kW.
- Utilisation d'un composé trinucléaire du molybdène soluble dans l'huile ou dispersable dans l'huile ou d'une composition comprenant le composé trinucléaire du molybdène pour réduire l'usure par corrosion dans une chemise de cylindre d'un moteur Diesel alimenté en huile combustible résiduelle.
- Procédé pour réduire l'usure par corrosion dans une chemise de cylindre d'un moteur Diesel alimenté en huile combustible résiduelle, comprenant l'amenée sur les parois du cylindre d'une composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 5.
- Composition d'additifs comprenant :(a) un composé trinucléaire du molybdène soluble dans l'huile ou dispersable dans l'huile ;(b) un ou plusieurs co-additifs ; et(c) une composition de détergent comprenant un ou plusieurs détergents à base de métaux surbasifiés ;
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02078107A EP1298190B1 (fr) | 2001-09-28 | 2002-07-30 | Compositions lubrifiantes pour la lubrification d'un moteur diesel marin |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01308354A EP1298189A1 (fr) | 2001-09-28 | 2001-09-28 | Composition lubrifiante pour la lubrification d'un moteur diesel marin |
EP01308354 | 2001-09-28 | ||
EP02078107A EP1298190B1 (fr) | 2001-09-28 | 2002-07-30 | Compositions lubrifiantes pour la lubrification d'un moteur diesel marin |
Publications (2)
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EP1298190A1 EP1298190A1 (fr) | 2003-04-02 |
EP1298190B1 true EP1298190B1 (fr) | 2005-10-12 |
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Application Number | Title | Priority Date | Filing Date |
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EP02078107A Expired - Lifetime EP1298190B1 (fr) | 2001-09-28 | 2002-07-30 | Compositions lubrifiantes pour la lubrification d'un moteur diesel marin |
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Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6642188B1 (en) * | 2002-07-08 | 2003-11-04 | Infineum International Ltd. | Lubricating oil composition for outboard engines |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2033923B (en) * | 1978-10-13 | 1982-12-22 | Exxon Research Engineering Co | Diesel lubricating oil compositions |
GB8602627D0 (en) * | 1986-02-04 | 1986-03-12 | Exxon Chemical Patents Inc | Marine lubricating composition |
US5629272A (en) * | 1991-08-09 | 1997-05-13 | Oronite Japan Limited | Low phosphorous engine oil compositions and additive compositions |
DE69525968T2 (de) * | 1994-12-20 | 2002-09-19 | Exxonmobil Res & Eng Co | Motoröl mit verbesserten eigenschaften zur kraftstoffersparnis |
EP0748365B1 (fr) * | 1994-12-28 | 2003-06-11 | Chevron Oronite Company LLC | Sulfonates de benzene oxy alkyle hyperbasiques utilises comme detergents |
US5744430A (en) * | 1995-04-28 | 1998-04-28 | Nippon Oil Co., Ltd. | Engine oil composition |
SG55446A1 (en) * | 1996-10-29 | 1998-12-21 | Idemitsu Kosan Co | Lube oil compositions for diesel engines |
US6277794B1 (en) * | 1998-12-28 | 2001-08-21 | Infineum Usa L.P. | Lubricant compositions |
US6143701A (en) * | 1998-03-13 | 2000-11-07 | Exxon Chemical Patents Inc. | Lubricating oil having improved fuel economy retention properties |
EP1087008B2 (fr) * | 1999-09-21 | 2008-08-06 | Infineum International Limited | Des compositions lubrifiantes multigrades de carter |
US6074993A (en) * | 1999-10-25 | 2000-06-13 | Infineuma Usa L.P. | Lubricating oil composition containing two molybdenum additives |
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2002
- 2002-07-30 EP EP02078107A patent/EP1298190B1/fr not_active Expired - Lifetime
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