EP3215591B1 - Compositions d'huiles lubrifiantes pour cylindres de moteurs diesel marins - Google Patents
Compositions d'huiles lubrifiantes pour cylindres de moteurs diesel marins Download PDFInfo
- Publication number
- EP3215591B1 EP3215591B1 EP15790598.5A EP15790598A EP3215591B1 EP 3215591 B1 EP3215591 B1 EP 3215591B1 EP 15790598 A EP15790598 A EP 15790598A EP 3215591 B1 EP3215591 B1 EP 3215591B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating oil
- marine diesel
- alkyl
- diesel cylinder
- oil composition
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 196
- 239000000314 lubricant Substances 0.000 title description 29
- -1 alkaline earth metal salts Chemical class 0.000 claims description 163
- 239000010687 lubricating oil Substances 0.000 claims description 115
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 71
- 150000003839 salts Chemical class 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 49
- 239000003599 detergent Substances 0.000 claims description 43
- 239000002270 dispersing agent Substances 0.000 claims description 41
- 239000000654 additive Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 21
- 229910052791 calcium Inorganic materials 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 230000001050 lubricating effect Effects 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 150000003752 zinc compounds Chemical class 0.000 claims description 6
- 230000000994 depressogenic effect Effects 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000006078 metal deactivator Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 description 81
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 56
- 239000003921 oil Substances 0.000 description 55
- 235000019198 oils Nutrition 0.000 description 54
- 239000004711 α-olefin Substances 0.000 description 34
- 150000001491 aromatic compounds Chemical class 0.000 description 33
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 32
- 125000004432 carbon atom Chemical group C* 0.000 description 27
- 230000000996 additive effect Effects 0.000 description 25
- 239000000446 fuel Substances 0.000 description 23
- 230000008569 process Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 21
- 239000003085 diluting agent Substances 0.000 description 21
- 239000012141 concentrate Substances 0.000 description 20
- 239000011593 sulfur Substances 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- 150000001412 amines Chemical class 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 238000005804 alkylation reaction Methods 0.000 description 16
- 239000002585 base Substances 0.000 description 16
- 239000002199 base oil Substances 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 230000029936 alkylation Effects 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000010763 heavy fuel oil Substances 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 229920000768 polyamine Chemical class 0.000 description 9
- 239000007848 Bronsted acid Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000000920 calcium hydroxide Substances 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 229960002317 succinimide Drugs 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 235000011116 calcium hydroxide Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 235000011044 succinic acid Nutrition 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229920002367 Polyisobutene Polymers 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 238000010924 continuous production Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 229920001281 polyalkylene Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 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 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002440 hydroxy compounds Chemical class 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000011968 lewis acid catalyst Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 125000006539 C12 alkyl 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
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- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
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- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 2
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
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- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- 230000035882 stress Effects 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
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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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives 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
- 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
- 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
- C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
-
- 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
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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
- 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
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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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
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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
- C10N2030/08—Resistance to extreme temperature
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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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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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
- C10N2030/40—Low content or no content compositions
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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
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
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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
Definitions
- the present invention generally relates to a marine diesel cylinder lubricating oil composition, in particular, for lubricating a marine two-stroke crosshead diesel cylinder engine.
- Diesel engines may generally be classified as low-speed, medium-speed, or high-speed engines, with the low-speed variety being used for the largest, deep shaft marine vessels and certain other industrial applications.
- Low-speed diesel engines are unique in size and method of operation.
- the engines themselves are massive, the larger units may approach 200 tons in weight and upward of 10 feet in length and 45 feet in height.
- the output of these engines can reach as high as 100,000 brake horsepower with engine revolutions of 60 to about 200 revolutions per minute. They are typically of crosshead design and operate on the two-stroke cycle.
- these engines usually operate on residual fuels, but some may also operate on distillate fuels that contain little or no residue.
- Medium-speed engines typically operate in the range of about 250 to about 1100 rpm and may operate on either the four-stroke or the two-stroke cycle.
- These engines can be of trunk piston design or occasionally of crosshead design. They usually operate on residual fuels, just like the low-speed diesel engines, but some may also operate on distillate fuels that contain little or no residue.
- These engines can also be used for propulsion, ancillary applications or both on deep-sea vessels.
- Low- and medium-speed diesel engines are also extensively used in power plant operations.
- a low- or medium-speed diesel engine that operates on the two-stroke cycle is typically a direct-coupled and direct-reversing engine of crosshead construction, with a diaphragm and one or more stuffing boxes separating the power cylinders from the crankcase to prevent combustion products from entering the crankcase and mixing with the crankcase oil.
- the notable complete separation of the crankcase from the combustion zone has led persons skilled in the art to lubricate the combustion chamber and the crankcase with different lubricating oils.
- 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.
- a primary function of marine diesel cylinder lubricants is to neutralize sulfur-based acidic components of high-sulfur fuel oil combusted in low-speed 2-stroke crosshead diesel engines.
- This neutralization is accomplished by the inclusion in the marine diesel cylinder lubricant of basic species such as metallic detergents.
- basic species such as metallic detergents.
- the basicity of the marine diesel cylinder lubricant can be diminished by oxidation of the marine diesel cylinder lubricant (caused by the thermal and oxidative stress the lubricant undergoes in the engine), thus decreasing the lubricant's neutralization ability.
- the oxidation can be accelerated if the marine diesel cylinder lubricants contain oxidation catalysts such as wear metals that are generally known to be present in the lubricant during engine operation.
- Marine two-stroke diesel cylinder lubricants must meet performance demands in order to comply with the severe operating conditions required for more modern larger bore, two-stroke cross-head diesel marine engines which are run at high outputs and severe loads and higher temperatures of the cylinder liner.
- Cylinder lubricant basicity, cylinder lubricant feed rate of the oil to the cylinder liner, engine make and type, engine load, inlet air humidity and fuel sulfur content are among the factors that can influence the amount of cold corrosion.
- High alkaline lubricants are used to neutralize the sulfuric acids and avoid cold corrosion of piston rings and cylinder liner surfaces.
- High alkalinity lubricants e.g., up to 100 BN by the ASTM D2896 test method) are currently being marketed to help overcome severe cold corrosion.
- Sulfurized, overbased phenates are known compounds which are widely used in marine applications for their detergency properties and thermal stability.
- low molecular weight alkylphenol compounds such as tetrapropenyl phenol (TPP) are often used as raw materials in the manufacture of these sulfurized, overbased phenates.
- TPP tetrapropenyl phenol
- the process to manufacture overbased phenates generally results in the presence of the unreacted alkylphenol in the final reaction product and ultimately in the finished lubricating oil composition.
- Recent reproductive toxicity studies have shown that in high concentrations of unreacted alkylphenol, TPP in particular, may be endocrine disruptive materials which can cause adverse effects in male and female reproductive organs.
- EP 1 126 010 A1 discloses a cylinder lubricating oil composition for marine diesel engines having high heat stability (hot tube test) and anti-wear performance at high temperatures.
- a marine diesel cylinder engine lubricating oil composition which comprises (a) a major amount of one or more Group II basestocks, and (b) a detergent composition comprising (i) 0.1 to 35 wt. % on an actives basis of one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a total base number (TBN) greater than 250, based on the total weight of the marine diesel cylinder lubricating oil composition, and(ii) 0.1 to 34 wt.
- TBN total base number
- a method for lubricating a marine two-stroke crosshead diesel engine comprising operating the engine with the marine diesel cylinder lubricating oil composition.
- a third embodiment of the present invention is directed to a use of the marine diesel cylinder lubricating oil composition for improving high temperature detergency and thermal stability in a two-stroke crosshead marine diesel engine.
- the present invention is based on the surprising discovery that the combination of one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, and one or more high overbased alkyl aromatic sulfonic acids or salts thereof advantageously improves the high temperature detergency and thermal stability of a marine diesel cylinder lubricating oil composition containing a major amount of one or more Group II basestocks and used in a two-stroke crosshead marine diesel engine; wherein the marine diesel cylinder lubricant has a TBN of from about 5 to about 120.
- the combination of the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, and one or more high overbased alkyl aromatic sulfonic acids or salts thereof also advantageously improves the storage stability of a marine diesel cylinder lubricating oil composition containing a major amount of one or more Group II basestocks, and having a TBN of from about 5 to about 120.
- marine diesel cylinder lubricant or "marine diesel cylinder lubricating oil” as used herein shall be understood to mean a lubricant used in the cylinder lubrication of a low speed or medium speed two-stroke crosshead marine diesel engine.
- the marine diesel cylinder lubricant is fed to the cylinder walls through a number of injection points.
- Marine diesel cylinder lubricants are capable of providing a film between the cylinder liner and the piston rings and holding partially burned fuel residues in suspension, to thereby promote engine cleanliness and neutralize acids formed by, for example, the combustion of sulfur compounds in the fuel.
- a “marine residual fuel” refers to a material combustible in large marine engines which has a carbon residue, as defined in International Organization for Standardization (ISO) 10370) of at least 2.5 wt. % (e.g., at least 5 wt. %, or at least 8 wt. %) (relative to the total weight of the fuel), a viscosity at 50°C of greater than 14.0 cSt, such as the marine residual fuels defined in the International Organization for Standardization specification ISO 8217:2005, "Petroleum products - Fuels (class F) - Specifications of marine fuels," the contents of which are incorporated herein in their entirety.
- ISO International Organization for Standardization
- a “residual fuel” refers to a fuel meeting the specification of a residual marine fuel as set forth in the ISO 8217:2010 international standard.
- a “low sulfur marine fuel” refers to a fuel meeting the specification of a residual marine fuel as set forth in the ISO 8217:2010 specification that, in addition, has about 1.5 wt. % or less, or even about 0.5% wt. % or less, of sulfur, relative to the total weight of the fuel.
- a “distillate fuel” refers to a fuel meeting the specification of a distillate marine fuel as set forth in the ISO 8217:2010 international standard.
- a “low sulfur distillate fuel” refers to a fuel meeting the specification of a distillate marine fuel set forth in the ISO 8217:2010 international standard that, in addition, has about 0.1 wt. % or less or even about 0.005 wt. % or less, of sulfur, relative to the total weight of the fuel.
- Bright stock refers to base oils that are direct products of de-asphalted petroleum vacuum residuum or derived from de-asphalted petroleum vacuum residuum after further processing such as solvent extraction and/or dewaxing. For the purposes of this invention, it also refers to deasphalted distillate cuts of a vacuum residuum process. Bright stocks generally have a kinematic viscosity at 100°C of from 28 to 36 mm 2 /s. One example of such a bright stock is ESSOTM Core 2500 Base Oil.
- Group II metal or "alkaline earth metal” means calcium, barium, magnesium, and strontium.
- calcium base refers to a calcium hydroxide, calcium oxide, calcium alkoxide and the like and mixtures thereof.
- lime refers to calcium hydroxide also known as slaked lime or hydrated lime.
- alkylphenol refers to a phenol group having one or more alkyl substituents at least one of which has a sufficient number of carbon atoms to impart oil solubility to the resulting phenate additive.
- phenate means a salt of a phenol.
- lower alkanoic acid refers to alkanoic acids having 1 through 3 carbon atoms, i.e., formic acid, acetic acid and propionic acid and mixtures thereof.
- polyol promoter refers to a compound having two or more hydroxy substituents, generally the sorbitol type, for example, alkylene glycols and also derivatives thereof and functional equivalents such as polyol ethers and hydroxycarboxylic acids.
- Total Base Number refers to the level of alkalinity in an oil sample, which indicates the ability of the composition to continue to neutralize corrosive acids, in accordance with ASTM Standard No. D2896 or equivalent procedure.
- the test measures the change in electrical conductivity, and the results are expressed as mgKOH/g (the equivalent number of milligrams of KOH needed to neutralize 1 gram of a product). Therefore, a high TBN reflects strongly overbased products and, as a result, a higher base reserve for neutralizing acids.
- base oil as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both.
- the term "on an actives basis” refers to additive material that is not diluent oil or solvent.
- isomerized olefins refers to olefins obtained by isomerizing olefins. Generally isomerized olefins have double bonds in different positions than the starting olefins from which they are derived, and may also have different characteristics.
- a marine diesel cylinder lubricating oil composition which comprises (a) a major amount of one or more Group II basestocks, and (b) a detergent composition comprising (i) one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, and (ii) one or more high overbased alkyl aromatic sulfonic acids or salts thereof; wherein the aromatic moiety of the alkyl aromatic sulfonic acids or salts thereof contains no hydroxyl groups; and wherein the marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 120.
- the marine diesel cylinder lubricating oil compositions of this invention will have a TBN of from about 5 to about 120. In one embodiment, the marine diesel cylinder lubricating oil compositions of this invention can have a TBN of from about 20 to about 100. In one embodiment, the marine diesel cylinder lubricating oil compositions of this invention can have a TBN of from about 40 to about 100. In one embodiment, the marine diesel cylinder lubricating oil compositions of this invention can have a TBN of from about 55 to about 80. In one embodiment, the marine diesel cylinder lubricating oil compositions of this invention can have a TBN of from about 60 to about 80.
- the marine diesel cylinder lubricating oil compositions of this invention can have a TBN of from about 10 to about 40. In one embodiment, the marine diesel cylinder lubricating oil compositions of this invention can have a TBN of from about 15 to about 35.
- the marine diesel cylinder lubricating oil composition of the present invention is substantially free of an unsulfurized tetrapropenyl phenol compound and its unsulfurized metal salt, e.g., TPP and its calcium salt.
- the term “substantially free” as used herein means relatively low levels, if any, of the unsulfurized tetrapropenyl phenol and its unsulfurized metal salt, e.g., less than about 1.5 wt. % in the marine diesel cylinder lubricating oil composition. In another embodiment, the term “substantially free” is less than about 1 wt. % in the marine diesel cylinder lubricating oil composition.
- the term “substantially free” is less than about 0.3 wt. % in the marine diesel cylinder lubricating oil composition. In another embodiment, the term “substantially free” is less than about 0.1 wt. % in the marine diesel cylinder lubricating oil composition. In another embodiment, the term “substantially free” is from about 0.0001 to about 0.3 wt. % in the marine diesel cylinder lubricating oil composition.
- the marine diesel cylinder lubricating oil compositions of this invention can have a kinematic viscosity ranging from about 12.5 to about 26.1 centistokes (cSt) at 100°C. In another embodiment, the lubricating oil composition has a viscosity of about 12.5 to about 21.9, or about 16.3 to about 21.9 cSt at 100°C.
- the kinematic viscosity of the marine diesel cylinder lubricating oil compositions is measured by ASTM D445.
- the marine diesel cylinder lubricating oil compositions of the present invention can be prepared by any method known to a person of ordinary skill in the art for making marine diesel cylinder lubricating oil compositions.
- the ingredients can be added in any order and in any manner. Any suitable mixing or dispersing equipment may be used for blending, mixing or solubilizing the ingredients.
- the blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., planetary mixers and double planetary mixers), a homogenizer (e.g., a Gaulin homogenizer or Rannie homogenizer), a mill (e.g., colloid mill, ball mill or sand mill) or any other mixing or dispersing equipment known in the art.
- a blender e.g., planetary mixers and double planetary mixers
- a homogenizer e.g., a Gaulin homogenizer or Rannie homogenizer
- a mill e.g., colloid mill, ball mill or sand mill
- any other mixing or dispersing equipment known in the art.
- the Group II basestocks for use herein can be any petroleum derived base oil of lubricating viscosity as defined in API Publication 1509, 14th Edition, Addendum I, Dec. 1998 .
- API guidelines define a base stock as a lubricant component that may be manufactured using a variety of different processes.
- a Group II basestock generally refers to a petroleum derived lubricating base oil having a total sulfur content equal to or less than 300 parts per million (ppm) (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), a saturates content equal to or greater than 90 weight percent (as determined by ASTM D 2007), and a viscosity index (VI) of between 80 and 120 (as determined by ASTM D 2270).
- ppm parts per million
- the one or more Group II basestocks can be a blend or mixture of two or more, three or more, or even four or more Group II basestocks having different molecular weights and viscosities, wherein the blend is processed in any suitable manner to create a base oil having suitable properties (such as the viscosity and TBN values, discussed above) for use in a marine diesel engine.
- the one or more Group II basestocks for use in the marine diesel engine lubricating oil compositions of this invention are typically present in a major amount, e.g., an amount greater than about 50 wt. %, or greater than about 70 wt. %, based on the total weight of the composition. In one embodiment, the one or more Group II basestocks are present in an amount of from 70 wt. % to about 95 wt. %, based on the total weight of the composition. In one embodiment, the one or more Group II basestocks are present in an amount of from 70 wt. % to about 85 wt. %, based on the total weight of the composition.
- the marine diesel engine lubricating oil compositions of the present invention can contain minor amounts of basestocks other than a Group II basestock.
- the marine diesel engine lubricating oil compositions can contain minor amounts of Groups I or III-V basestocks as defined in API Publication 1509, 16th Edition, Addendum I, Oct., 2009 .
- Group IV base oils are polyalphaolefins (PAO).
- the marine diesel cylinder lubricating oil compositions for use in marine diesel engines typically have a kinematic viscosity in the range of 12.5 to 26.1 cSt at 100°C.
- a bright stock may be combined with a low viscosity oil, e.g., an oil having a viscosity from 4 to 6 cSt at 100°C.
- supplies of bright stock are dwindling and therefore bright stock cannot be relied upon to increase the viscosity of marine cylinder lubricants to the desired ranges that manufacturers recommend.
- PIB polyisobutylene
- viscosity index improver compounds such as olefin copolymers
- PIB is a commercially available material from several manufacturers.
- the PIB is typically a viscous oil-miscible liquid, having a weight average molecular weight in the range of about 1,000 to about 8,000, or from about 1,500 to about 6,000, and a viscosity in the range of about 2,000 to about 5,000 or about 6,000 cSt (at 100°C).
- the amount of PIB added to the marine diesel cylinder lubricating oil compositions will normally be from about 1 to about 20 wt. % of the finished oil, or from about 2 to about 15 wt. % of the finished oil, or from about 4 to about 12 wt. % of the finished oil.
- Group I base oils generally refer to a petroleum derived lubricating base oil having a saturates content of less than 90 wt. % (as determined by ASTM D 2007) and/or a total sulfur content of greater than 300 ppm (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4297 or ASTM D 3120) and has a viscosity index (VI) of greater than or equal to 80 and less than 120 (as determined by ASTM D 2270).
- Group I base oils can comprise light overhead cuts and heavier side cuts from a vacuum distillation column and can also include, for example, Light Neutral, Medium Neutral, and Heavy Neutral base stocks.
- the petroleum derived base oil also may include residual stocks or bottoms fractions, such as, for example, bright stock.
- Bright stock is a high viscosity base oil which has been conventionally produced from residual stocks or bottoms and has been highly refined and dewaxed. Bright stock can have a kinematic viscosity greater than about 180 cSt at 40°C, or even greater than about 250 cSt at 40°C, or even ranging from about 500 to about 1100 cSt at 40°C.
- a Group I basestock comprises ExxonMobil CORE®100, ExxonMobil CORE®150, ExxonMobil CORE®600, or ExxonMobil CORE®2500, or mixture thereof.
- a Group III basestock generally has a total sulfur content less than or equal to 0.03 wt. % (as determined by ASTM D 2270), a saturates content of greater than or equal to 90 wt. % (as determined by ASTM D 2007), and a viscosity index (VI) of greater than or equal to 120 (as determined by ASTM D 4294, ASTM D 4297 or ASTM D 3120).
- the basestock is a Group III basestock, or a blend of two or more different Group III basestocks.
- Group III basestocks derived from petroleum oils are severely hydrotreated mineral oils. Hydrotreating involves reacting hydrogen with the basestock to be treated to remove heteroatoms from the hydrocarbon, reduce olefins and aromatics to alkanes and cycloparaffins respectively, and in very severe hydrotreating, open up naphthenic ring structures to non-cyclic normal and iso-alkanes ("paraffins").
- a Group III basestock has a paraffinic carbon content (% C p ) of at least about 70 %, as determined by test method ASTM D 3238-95 (2005), "Standard Test Method for Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by the n-d-M Method".
- a Group III basestock has a paraffinic carbon content (% C p ) of at least about 72 %. In another embodiment, a Group III basestock has a paraffinic carbon content (% C p ) of at least about 75 %. In another embodiment, a Group III basestock has a paraffinic carbon content (% C p ) of at least about 78 %. In another embodiment, a Group III basestock has a paraffinic carbon content (% C p ) of at least about 80 %. In another embodiment, a Group III basestock has a paraffinic carbon content (% C p ) of at least about 85 % .
- a Group III basestock has a naphthenic carbon content (% C n ) of no more than about 25 %, as determined by ASTM D 3238-95 (2005). In another embodiment, a Group III basestock has a naphthenic carbon content (% C n ) of no more than about 20 %. In another embodiment, a Group III basestock has a naphthenic carbon content (% C n ) of no more than about 15 %. In another embodiment, a Group III basestock has a naphthenic carbon content (% C n ) of no more than about 10 %.
- Group III basestocks are available commercially, e.g., Chevron UCBO basestocks; Yukong Yubase basestocks; Shell XHVI® basestocks; and ExxonMobil Exxsyn® basestocks.
- a Group III basestock for use herein is a Fischer-Tropsch derived base oil.
- Fischer-Tropsch derived means that the product, fraction, or feed originates from or is produced at some stage by a Fischer-Tropsch process.
- a Fischer Tropsch base oil can be produced from a process in which the feed is a waxy feed recovered from a Fischer-Tropsch synthesis, see, e.g., U.S. Patent Application Publication Nos.
- the process involves a complete or partial hydroisomerization dewaxing step, employing a dual-functional catalyst or a catalyst that can isomerize paraffins selectively.
- Hydroisomerization dewaxing is achieved by contacting the waxy feed with a hydroisomerization catalyst in an isomerization zone under hydroisomerizing conditions.
- Fischer-Tropsch synthesis products can be obtained by well-known processes such as, for example, the commercial SASOL® Slurry Phase Fischer-Tropsch technology, the commercial SHELL® Middle Distillate Synthesis (SMDS) Process, or by the non-commercial EXXON® Advanced Gas Conversion (AGC-21) process. Details of these processes and others are described in, for example, WO-A-9934917 ; WO-A-9920720 ; WO-A-05107935 ; EP-A- 776959 ; EP-A-668342 ; U.S. Patent Nos. 4,943,672 , 5,059,299 ; 5,733,839 ; and RE39073 ; and U.S. Patent Application Publication No. 2005/0227866 .
- the Fischer-Tropsch synthesis product can contain hydrocarbons having 1 to about 100 carbon atoms or, in some cases, more than 100 carbon atoms, and typically includes paraffins, olefins and oxygenated products.
- a Group IV basestock, or polyalphaolefin (PAO) are typically made by the oligomerization of low molecular weight alpha-olefins, e.g., alpha-olefins containing at least 6 carbon atoms.
- the alpha-olefins are alpha-olefins containing 10 carbon atoms.
- PAOs are mixtures of dimers, trimers, tetramers, etc., with the exact mixture depending upon the viscosity of the final basestock desired.
- PAOs are typically hydrogenated after oligomerization to remove any remaining unsaturation.
- Group V base oils include all other base oils not included in Group I, II, III, or IV.
- the marine diesel cylinder lubricating oil compositions of the present invention further comprise a detergent composition comprising (i) one or more alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250, and (ii) one or more high overbased alkyl aromatic sulfonic acids or salts thereof; wherein the aromatic moiety of the alkyl aromatic sulfonic acids or salts thereof contains no hydroxyl groups.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid and the one or more high overbased alkyl aromatic sulfonic acids or salts thereof are provided as a concentrate in each of the additives are incorporated into a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate.
- a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate.
- These concentrates usually contain from about 10% to about 90% by weight of such diluent or from about 20% to about 80% by weight of such diluent, with the remaining amount being the specific additive.
- a neutral oil having a viscosity of about 4 to about 8.5 cSt at 100°C and preferably about 4 to about 6 cSt at 100°C will be used as the diluent, though synthetic oils, as well as other organic liquids which are compatible with the additives and finished lubricating oil can also be used.
- the concentrate is substantially free of an unsulfurized tetrapropenyl phenol compound and its unsulfurized metal salt, e.g., TPP and its calcium salt.
- the term “substantially free” as used herein means relatively low levels, if any, of the unsulfurized tetrapropenyl phenol and its unsulfurized metal salt, e.g., less than about 1.5 wt. % in the concentrate. In another embodiment, the term “substantially free” is less than about 1 wt. % in the concentrate. In another embodiment, the term “substantially free” is less than about 0.3 wt. % in the concentrate. In another embodiment, the term “substantially free” is less than about 0.1 wt. % in the concentrate. In another embodiment, the term “substantially free” is from about 0.0001 to about 0.3 wt. % in the concentrate.
- the detergent composition employed in the marine diesel cylinder lubricating oil compositions of the present invention includes one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250.
- the TBN of the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid are on an actives basis.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greater than 250 and up to about 800.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greater than 250 and up to about 750. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greater than 250 and up to about 700. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greater than 250 and up to about 650.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greater than 250 and up to about 600. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greater than 250 and up to about 410.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 260 to about 800. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 260 to about 750. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 260 to about 700.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 260 to about 650. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 260 to about 600. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 260 and up to about 410.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greater than or equal to about 300. In another embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 300 to about 800. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 300 to about 750.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 300 to about 700. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 300 to about 650. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 300 to about 600. In one embodiment, the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid have a TBN of from about 300 to about 410.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid are one or more alkaline earth metal salts of an alkyl-substituted hydroxybenzoic acid having a TBN of greater than 250.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid are calcium alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of greater than 250.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid has a major amount of one or more alkaline earth metal salts of mono-alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid are one or more alkaline earth metal salts of an alkyl-substituted hydroxybenzoic acid having a TBN of greater than or equal to about 300.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid are calcium alkyl-substituted hydroxyaromatic carboxylic acids having a TBN of greater than or equal to about 300.
- the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid has a major amount of one or more alkaline earth metal salts of mono-alkyl-substitutedhydroxyaromatic carboxylic acid having a TBN of greater than or equal to about 300.
- Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups.
- Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
- the preferred hydroxyaromatic compound is phenol.
- the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid can be derived from an alpha olefin having from about 10 to about 80 carbon atoms. In one embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid can be derived from an alpha olefin having from about 10 to about 40 carbon atoms.
- the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid can be derived from an alpha olefin having from about 12 to about 28 carbon atoms.
- the olefins employed may be linear, isomerized linear, branched or partially branched linear.
- the olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear or a mixture of any of the foregoing.
- the mixture of linear olefins that may be used is a mixture of normal alpha olefins selected from olefins having from about 12 to about 28, or about 20 to 28, carbon atoms per molecule.
- the normal alpha olefins are isomerized using at least one of a solid or liquid catalyst.
- the olefins include one or more olefins comprising C 9 to C 18 oligomers of monomers selected from propylene, butylene or mixtures thereof.
- the one or more olefins will contain a major mount of the C 9 to C 18 oligomers of monomers selected from propylene, butylene or mixtures thereof.
- examples of such olefins include propylene tetramer, butylene trimer and the like. As one skilled in the art will readily appreciate, other olefins may be present.
- the other olefins that can be used in addition to the C 9 to C 18 oligomers include linear olefins, cyclic olefins, branched olefins other than propylene oligomers such as butylene or isobutylene oligomers, arylalkylenes and the like and mixtures thereof.
- Suitable linear olefins include 1-hexene, 1-nonene, 1-decene, 1-dodecene and the like and mixtures thereof.
- Especially suitable linear olefins are high molecular weight normal alpha-olefins such as C 16 to C 30 normal alpha-olefins, which can be obtained from processes such as ethylene oligomerization or wax cracking.
- Suitable cyclic olefins include cyclohexene, cyclopentene, cyclooctene and the like and mixtures thereof.
- Suitable branched olefins include butylene dimer or trimer or higher molecular weight isobutylene oligomers, and the like and mixtures thereof.
- Suitable arylalkylenes include styrene, methyl styrene, 3-phenylpropene, 2-phenyl-2-butene and the like and mixtures thereof.
- the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid can contain a mixture of C 12 alkyl groups and C 20 to C 28 linear olefins. In one embodiment, the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid can contain up to about 50% by weight of C 12 alkyl groups in mixture with at least about 50% by weight of C 20 to C 28 linear olefins.
- the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid can contain up to 50% by weight of C 20 to C 28 linear olefins in mixture with at least 50% by weight of a branched hydrocarbyl radical derived from propylene oligomer.
- the alkyl-substituted moiety of the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid can contain up to 85% by weight of C 20 to C 28 linear olefins in mixture with at least 15% by weight of a branched hydrocarbyl radical derived from propylene oligomer.
- At least about 75 mole% (e.g., at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 95 mole%, or at least about 99 mole%) of the alkyl groups contained within the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid are C 20 alkyl groups or higher.
- the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid that is derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl groups are the residue of normal alpha-olefins containing at least 75 mole% C 20 or higher normal alpha-olefins.
- At least about 50 mole % (e.g., at least about 60 mole %, at least about 70 mole %, at least about 80 mole %, at least about 85 mole %, at least about 90 mole %, at least about 95 mole %, or at least about 99 mole %) of the alkyl groups contained within the alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid are about C 14 to about C 18 .
- the resulting alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 can be a mixture of ortho and para isomers.
- the product will contain about 1 to 99% ortho isomer and 99 to 1% para isomer. In another embodiment, the product will contain about 5 to 70% ortho and 95 to 30% para isomer.
- the alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid are one in which the BN of the alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid has been increased by a process such as the addition of a base source (e.g., lime) and an acidic overbasing compound (e.g., carbon dioxide).
- a base source e.g., lime
- an acidic overbasing compound e.g., carbon dioxide
- the amount of the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 present in a marine diesel cylinder lubricating oil composition having a TBN of about 5 to about 120 ranges from about 0.1 wt. % to about 35 wt. % on an actives basis, based on the total weight of the marine diesel cylinder lubricating oil composition.
- the amount of the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 present in the marine diesel cylinder lubricating oil composition a marine diesel cylinder lubricating oil composition having a TBN of about 20 to about 100 can range from about 1 wt. % to about 25 wt. % on an actives basis, based on the total weight of the marine diesel cylinder lubricating oil composition.
- the amount of the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 present in the marine diesel cylinder lubricating oil composition a also marine diesel cylinder lubricating oil composition having a TBN of about 20 to about 60 can range from about 3 wt. % to about 20 wt. % on an actives basis, based on the total weight of the marine diesel cylinder lubricating oil composition.
- the amount of the one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 present in the marine diesel cylinder lubricating oil composition a marine diesel cylinder lubricating oil composition having a TBN of about 30 to about 50 can range from about 3 wt. % to about 15 wt. % on an actives basis, based on the total weight of the marine diesel cylinder lubricating oil composition.
- the detergent composition employed in the marine diesel cylinder lubricating oil compositions of the present invention also includes one or more high overbased alkyl aromatic sulfonic acids or salts thereof.
- the alkyl aromatic sulfonic acids or salts thereof include alkyl aromatic sulfonic acids or salts thereof obtained by the alkylation of an aromatic compound.
- the alkyl aromatic compound is then sulfonated to form an alkyl aromatic sulfonic acid.
- the alkyl aromatic sulfonic acid can be neutralized with caustic to obtain an alkali or alkaline earth metal alkyl aromatic sulfonate compound.
- At least one aromatic compound or a mixture of aromatic compounds may be used to form the alkyl aromatic sulfonic acid or salt thereof.
- Suitable aromatic compounds or the aromatic compound mixture comprise at least one of monocyclic aromatics, such as benzene, toluene, xylene, cumene or mixtures thereof.
- the at least one aromatic moiety of the alkyl aromatic sulfonic acids or salts contains no hydroxyl groups.
- the at least one aromatic moiety of the alkyl aromatic sulfonic acids or salts compound is not a phenol.
- the at least one aromatic compound or aromatic compound mixture is toluene.
- the at least one alkyl aromatic compound or the mixture of aromatic compounds is commercially available or may be prepared by methods that are well known in the art.
- the alkylating agent employed to alkylate the aromatic compound may be derived from a variety of sources. Such sources include the normal alpha olefins, linear alpha olefins, isomerized linear alpha olefins, dimerized and oligomerized olefins, and olefins derived from olefin metathesis.
- the olefin may be a single carbon number olefin, or it may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched olefins, or a mixture of any of the foregoing.
- olefins Another source from which the olefins may be derived is through cracking of petroleum or Fischer-Tropsch wax.
- the Fischer-Tropsch wax may be hydrotreated prior to cracking.
- Other commercial sources include olefins derived from paraffin dehydrogenation and oligomerization of ethylene and other olefins, methanol-to-olefin processes (methanol cracker) and the like.
- the olefins may selected from olefins with carbon numbers ranging from about 8 carbon atoms to about 60 carbon atoms. In one embodiment, the olefins are selected from olefins with carbon numbers ranging from about 10 to about 50 carbon atoms. In one embodiment, the olefins are selected from olefins with carbon numbers ranging from about 12 to about 40 carbon atoms.
- the olefin or the mixture of olefins is selected from linear alpha olefins or isomerized alpha olefins containing from about 8 to about 60 carbon atoms. In one embodiment, the mixture of olefins is selected from linear alpha olefins or isomerized alpha olefins containing from about 10 to about 50 carbon atoms. In one embodiment, the mixture of olefins is selected from linear alpha olefins or isomerized olefins containing from about 12 to about 40 carbon atoms.
- the linear olefins that may be used for the alkylation reaction may be one or a mixture of normal alpha olefins selected from olefins having from about 8 to about 60 carbon atoms per molecule. In one embodiment, the normal alpha olefin is selected from olefins having from about 10 to about 50 carbon atoms per molecule. In one embodiment, the normal alpha olefin is selected from olefins having from about 12 to about 40 carbon atoms per molecule.
- the mixture of branched olefins is selected from polyolefins which may be derived from C 3 or higher monoolefins (e.g., propylene oligomers, butylenes oligomers, or co-oligomers etc.). In one embodiment, the mixture of branched olefins is either propylene oligomers or butylenes oligomers or mixtures thereof.
- the aromatic compound is alkylated with a mixture of normal alpha olefins containing from C 8 to C 60 carbon atoms. In one embodiment, the aromatic compound is alkylated with a mixture of normal alpha olefins containing from C 10 to C 50 carbon atoms. In another embodiment, the aromatic compound is alkylated with a mixture of normal alpha olefins containing from C 12 to C 40 carbon atoms to yield an aromatic alkylate.
- the normal alpha olefins employed to make the alkylaromatic sulfonic acid or salt thereof are commercially available or may be prepared by methods that are well known in the art.
- the normal alpha olefins are isomerized using a solid or a liquid acid catalyst.
- a solid catalyst preferably has at least one metal oxide and an average pore size of less than 5.5 angstroms.
- the solid catalyst is a molecular sieve with a one-dimensional pore system, such as SM-3, MAPO-11, SAPO-11, SSZ-32, ZSM-23, MAPO-39, SAPO-39, ZSM-22 or SSZ-20.
- Other possible acidic solid catalysts useful for isomerization include ZSM-35, SUZ-4, NU-23, NU-87 and natural or synthetic ferrierites.
- a liquid type of isomerization catalyst that can be used is iron pentacarbonyl (Fe(CO) 5 ).
- the process for isomerization of normal alpha olefins may be carried out in batch or continuous mode.
- the process temperatures may range from about 50°C to about 250°C.
- a typical method used is a stirred autoclave or glass flask, which may be heated to the desired reaction temperature.
- a continuous process is most efficiently carried out in a fixed bed process. Space rates in a fixed bed process can range from about 0.1 to about 10 or more weight hourly space velocity.
- the isomerization catalyst In a fixed bed process, the isomerization catalyst is charged to the reactor and activated or dried at a temperature of at least 125°C under vacuum or flowing inert, dry gas. After activation, the temperature of the isomerization catalyst is adjusted to the desired reaction temperature and a flow of the olefin is introduced into the reactor. The reactor effluent containing the partially-branched, isomerized olefins is collected.
- the resulting partially-branched, isomerized olefins contain a different olefin distribution (i.e., alpha olefin, beta olefin; internal olefin, tri-substituted olefin, and vinylidene olefin) and branching content than that of the unisomerized olefin and conditions are selected in order to obtain the desired olefin distribution and the degree of branching.
- olefin distribution i.e., alpha olefin, beta olefin; internal olefin, tri-substituted olefin, and vinylidene olefin
- the alkylated aromatic compound may be prepared using a Bronsted acid catalyst, a Lewis acid catalyst, or solid acidic catalysts.
- the Bronsted acid catalyst may be selected from a group comprising hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, perchloric acid, trifluoromethane sulfonic acid, fluorosulfonic acid, and nitric acid and the like.
- the Bronsted acid catalyst is hydrofluoric acid.
- the Lewis acid catalyst may be selected from the group of Lewis acids comprising aluminum trichloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, boron triiodide and the like.
- the Lewis acid catalyst is aluminum trichloride.
- the solid acidic catalysts may be selected from a group comprising zeolites, acid clays, and/or silica-alumina.
- An eligible solid catalyst is a cation exchange resin in its acid form, for example, crosslinked sulfonic acid catalyst.
- the catalyst may be a molecular sieve. Suitable molecular sieves are silica-aluminophosphate molecular sieves or metal silica-aluminophosphate molecular sieves, in which the metal may be, for example, iron, cobalt or nickel.
- Other suitable examples of solid acidic catalysts are disclosed in U.S. Patent No. 7,183,452 .
- the Bronsted acid catalyst may be regenerated after it becomes deactivated (i.e., the catalyst has lost all or some portion of its catalytic activity). Methods that are well known in the art may be used to regenerate the acid catalyst, for example, hydrofluoric acid.
- the alkylation technologies used to produce the alkyl aromatic will include Bronsted and/or Lewis acids as well as solid acid catalysts utilized in a batch, semi-batch or continuous process operating at between from about 0 to about 300°C.
- the acid catalyst may be recycled when used in a continuous process.
- the acid catalyst may be recycled or regenerated when used in a batch process or a continuous process.
- the alkylation process is carried out by reacting a first amount of at least one aromatic compound or a mixture of aromatic compounds with a first amount of a mixture of olefin compounds in the presence of a Bronsted acid catalyst, such as hydrofluoric acid, in a first reactor in which agitation is maintained, thereby producing a first reaction mixture.
- a Bronsted acid catalyst such as hydrofluoric acid
- the resulting first reaction mixture is held in a first alkylation zone under alkylation conditions for a time sufficient to convert the olefin to aromatic alkylate (i.e., a first reaction product).
- the first reaction product is removed from the alkylation zone and fed to a second reactor wherein the first reaction product is reacted with an additional amount of at least one aromatic compound or a mixture of aromatic compounds and an additional amount of acid catalyst and, optionally, with an additional amount of a mixture of olefin compounds wherein agitation is maintained.
- a second reaction mixture results and is held in a second alkylation zone under alkylation conditions for a time sufficient to convert the olefin to aromatic alkylate (i.e., a second reaction product).
- the second reaction product is fed to a liquid-liquid separator to allow hydrocarbon (i.e., organic) products to separate from the acid catalyst.
- the acid catalyst may be recycled to the reactor(s) in a closed loop cycle.
- the hydrocarbon product is further treated to remove excess un-reacted aromatic compounds and, optionally, olefinic compounds from the desired alkylate product. The excess aromatic compounds may also be recycled to the reactor(s).
- the reaction takes place in more than two reactors which are located in series.
- the second reaction product is fed to a third reactor wherein the second reaction product is reacted with an additional amount of at least one aromatic compound or a mixture of aromatic compounds and an additional amount of acid catalyst and, optionally, with an additional amount of a mixture of olefin compounds wherein agitation is maintained.
- a third reaction mixture results and is held in a third alkylation zone under alkylation conditions for a time sufficient to convert the olefin to aromatic alkylate (i.e., a third reaction product).
- the reactions take place in as many reactors as necessary to obtain the desired alkylated aromatic reaction product.
- the total charge mole ratio of Bronsted acid catalyst to the olefin compounds is about 0.1 to about 1 for the combined reactors. In one embodiment, the charge mole ratio of Bronsted acid catalyst to the olefin compounds is no more than about 0.7 to about 1 in the first reactor and no less than about 0.3 to about 1 in the second reactor.
- the total charge mole ratio of the aromatic compound to the olefin compounds is about 7.5:1 to about 1:1 for the combined reactors. In one embodiment, the charge mole ratio of the aromatic compound to the olefin compounds is no less than about 1.4:1 to about 1:1 in the first reactor and is no more than about 6.1:1 to about 1:1 in the second reactor.
- reactor configurations may be used for the reactor zone. These include, but are not limited to, batch and continuous stirred tank reactors, reactor riser configurations, ebulating bed reactors, and other reactor configurations that are well known in the art. Many such reactors are known to those skilled in the art and are suitable for the alkylation reaction. Agitation is critical for the alkylation reaction and can be provided by rotating impellers, with or without baffles, static mixers, kinetic mixing in risers, or any other agitation devices that are well known in the art.
- the alkylation process may be carried out at temperatures from about 0°C to about 100°C. The process is carried out under sufficient pressure that a substantial portion of the feed components remain in the liquid phase. Typically, a pressure of 0 to 150 psig is satisfactory to maintain feed and products in the liquid phase.
- the residence time in the reactor is a time that is sufficient to convert a substantial portion of the olefin to alkylate product.
- the time required is from about 30 seconds to about 30 minutes.
- a more precise residence time may be determined by those skilled in the art using batch stirred tank reactors to measure the kinetics of the alkylation process.
- the at least one aromatic compound or mixture of aromatic compounds and the olefin compounds may be injected separately into the reaction zone or may be mixed prior to injection. Both single and multiple reaction zones may be used with the injection of the aromatic compounds and the olefin compounds into one, several, or all reaction zones. The reaction zones need not be maintained at the same process conditions.
- the hydrocarbon feed for the alkylation process may comprise a mixture of aromatic compounds and olefin compounds in which the molar ratio of aromatic compounds to olefins is from about 0.5:1 to about 50:1 or more. In the case where the molar ratio of aromatic compounds to olefin is >1.0 to 1, there is an excess amount of aromatic compounds present. In one embodiment, an excess of aromatic compounds is used to increase reaction rate and improve product selectivity. When excess aromatic compounds are used, the excess un-reacted aromatic in the reactor effluent can be separated, e.g., by distillation, and recycled to the reactor.
- the alkyl aromatic product is obtained as described above, it is further reacted to form an alkyl aromatic sulfonic acid, and can then be neutralized to the corresponding sulfonate.
- Sulfonation of the alkyl aromatic compound may be performed by any method known to one of ordinary skill in the art.
- the sulfonation reaction is typically carried out in a continuous falling film tubular reactor maintained at about 45°C to about 75°C.
- the alkyl aromatic compound is placed in the reactor along with sulfur trioxide diluted with air thereby producing an alkylaryl sulfonic acid.
- Other sulfonation reagents such as sulfuric acid, chlorosulfonic acid or sulfamic acid may also be employed.
- the alkyl aromatic compound is sulfonated with sulfur trioxide diluted with air.
- the charge mole ratio of sulfur trioxide to alkylate is maintained at about 0.8 to about 1.1:1.
- neutralization of the alkyl aromatic sulfonic acid may be carried out in a continuous or batch process by any method known to a person skilled in the art to produce alkyl aromatic sulfonates.
- an alkyl aromatic sulfonic acid is neutralized with a source of alkali or alkaline earth metal or ammonia, thereby producing an alkyl aromatic sulfonate.
- suitable alkali metals include lithium, sodium, potassium, rubidium, and cesium.
- a suitable alkali metal includes sodium and potassium.
- a suitable alkali metal is sodium.
- suitable alkaline earth metals include calcium, barium, magnesium, or strontium and the like.
- a suitable alkaline earth metal is calcium.
- the source is an alkali metal base such as an alkali metal hydroxide, e.g., sodium hydroxide or potassium hydroxide.
- the source is an alkaline earth metal base such as an alkaline earth metal hydroxide, e.g., calcium hydroxide.
- the one or more alkyl aromatic sulfonic acid or salts thereof are one or more high overbased alkyl aromatic sulfonic acid or salts thereof.
- overbasing is one in which the TBN of the alkyl aromatic sulfonic acid or salts thereof has been increased by a process such as, for example, the addition of a base source (e.g., lime) and an acidic overbasing compound (e.g., carbon dioxide).
- a base source e.g., lime
- an acidic overbasing compound e.g., carbon dioxide
- the one or more high overbased alkyl aromatic sulfonic acids or salts thereof has a TBN greater than 250. In one embodiment, the one or more high overbased alkyl aromatic sulfonic acids or salts thereof will have a TBN up to about 700. In one embodiment, the one or more high overbased alkyl aromatic sulfonic acids or salts thereof will have a TBN greater than or equal to about 300. In one embodiment, the one or more high overbased alkyl aromatic sulfonic acids or salts thereof will have a TBN of about 300 to about 700.
- the amount of the one or more high overbased alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricating oil composition having a TBN of about 5 to about 120 ranges from about 0.1 wt. % to about 34 wt. % on an actives basis, based on the total weight of the marine diesel cylinder lubricating oil composition.
- the amount of the one or more high overbased alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricating oil composition having a TBN of about 20 to about 100 can range from about 1 wt. % to about 30 wt.
- the amount of the one or more high overbased alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricating oil composition having a TBN of about 20 to about 60 can range from about 2 wt. % to about 24 wt. % on an actives basis, based on the total weight of the marine diesel cylinder lubricating oil composition. In one embodiment, the amount of the one or more high overbased alkyl aromatic sulfonic acids or salts thereof present in a marine diesel cylinder lubricating oil composition having a TBN of about 30 to about 50 can range from about 5 wt. % to about 16 wt. % on an actives basis, based on the total weight of the marine diesel cylinder lubricating oil composition.
- the marine diesel cylinder lubricating oil compositions of the present invention may also contain conventional marine diesel cylinder lubricating oil composition additives, other than the foregoing one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 and the one or more high overbased alkyl aromatic sulfonic acids or salts thereof, for imparting auxiliary functions to give a marine diesel cylinder lubricating oil composition in which these additives are dispersed or dissolved.
- conventional marine diesel cylinder lubricating oil composition additives other than the foregoing one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of greater than 250 and the one or more high overbased alkyl aromatic sulfonic acids or salts thereof, for imparting auxiliary functions to give a marine diesel cylinder lubricating oil composition in which these additives are dispersed or dissolved.
- the marine diesel cylinder lubricating oil compositions can be blended with antioxidants, ashless dispersants, other detergents, anti-wear agents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, cosolvents, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof.
- antioxidants ashless dispersants, other detergents, anti-wear agents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, cosolvents, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof.
- additives are known and commercially available. These additives, or their analogous compounds, can be employed for the preparation of the marine diesel cylinder lubricating oil compositions of the invention by the usual blending procedures.
- the marine diesel cylinder lubricating oil compositions of the present invention contain essentially no thickener (i.e., a viscosity index improver).
- antioxidants include, but are not limited to, aminic types, e.g., diphenylamine, phenyl-alpha-napthyl-amine, N,N-di(alkylphenyl) amines; and alkylated phenylene-diamines; phenolics such as, for example, BHT, sterically hindered alkyl phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-(2-octyl-3-propanoic) phenol; and mixtures thereof.
- aminic types e.g., diphenylamine, phenyl-alpha-napthyl-amine, N,N-di(alkylphenyl) amines
- alkylated phenylene-diamines alkylated phenylene-diamines
- the ashless dispersant compounds employed in the marine diesel cylinder lubricating oil compositions of the present invention are generally used to maintain in suspension insoluble materials resulting from oxidation during use, thus preventing sludge flocculation and precipitation or deposition on metal parts. Dispersants may also function to reduce changes in lubricating oil viscosity by preventing the growth of large contaminant particles in the lubricant.
- the dispersant employed in the present invention may be any suitable ashless dispersant or mixture of multiple ashless dispersants for use in a marine diesel cylinder lubricating oil composition.
- An ashless dispersant generally comprises an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
- an ashless dispersant is one or more basic nitrogen-containing ashless dispersants.
- Nitrogen-containing basic ashless (metal-free) dispersants contribute to the base number or BN (as can be measured by ASTM D 2896) of a lubricating oil composition to which they are added, without introducing additional sulfated ash.
- Basic nitrogen-containing ashless dispersants useful in this invention include hydrocarbyl succinimides; hydrocarbyl succinamides; mixed ester/amides of hydrocarbyl-substituted succinic acids formed by reacting a hydrocarbyl-substituted succinic acylating agent stepwise or with a mixture of alcohols and amines, and/or with amino alcohols; Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines; and amine dispersants formed by reacting high molecular weight aliphatic or alicyclic halides with amines, such as polyalkylene polyamines. Mixtures of such dispersants can also be used.
- ashless dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbones via bridging groups.
- An ashless dispersant of the present invention 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 Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
- Carboxylic dispersants are reaction products of carboxylic acylating agents (acids, anhydrides, esters, etc.) comprising at least about 34 and preferably at least about 54 carbon atoms with nitrogen containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols), and/or basic inorganic materials.
- carboxylic acylating agents as acids, anhydrides, esters, etc.
- nitrogen containing compounds such as amines
- organic hydroxy compounds such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols
- basic inorganic materials include imides, amides, and esters.
- Succinimide dispersants are a type of carboxylic dispersant. They are produced by reacting hydrocarbyl-substituted succinic acylating agent with organic hydroxy compounds, or with amines comprising at least one hydrogen atom attached to a nitrogen atom, or with a mixture of the hydroxy compounds and amines.
- succinic acylating agent refers to a hydrocarbon-substituted succinic acid or a succinic acid-producing compound, the latter encompasses the acid itself.
- Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.
- Succinic-based dispersants have a wide variety of chemical structures.
- One class of succinic-based dispersants may be represented by the formula: wherein each R 1 is independently a hydrocarbyl group, such as a polyolefin-derived group. Typically the hydrocarbyl group is an alkyl group, such as a polyisobutyl group. Alternatively expressed, the R 1 groups can contain about 40 to about 500 carbon atoms, and these atoms may be present in aliphatic forms.
- R 2 is an alkylene group, commonly an ethylene (C 2 H 4 ) group.
- succinimide dispersants include those described in, for example, U.S. Patent Nos. 3,172,892 , 4,234,435 and 6,165,235 .
- the polyalkenes from which the substituent groups are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms, and usually 2 to 6 carbon atoms.
- the amines which are reacted with the succinic acylating agents to form the carboxylic dispersant composition can be monoamines or polyamines.
- Succinimide dispersants are referred to as such since they normally contain nitrogen largely in the form of imide functionality, although the amide functionality may be in the form of amine salts, amides, imidazolines as well as mixtures thereof.
- a succinimide dispersant one or more succinic acid-producing compounds and one or more amines are heated and typically water is removed, optionally in the presence of a substantially inert organic liquid solvent/diluent.
- the reaction temperature can range from about 80°C up to the decomposition temperature of the mixture or the product, which typically falls between about 100°C to about 300°C. Additional details and examples of procedures for preparing the succinimide dispersants of the present invention include those described in, for example, U.S. Patent Nos. 3,172,892 , 3,219,666 , 3,272,746 , 4,234,435 , 6,165,235 and 6,440,905 .
- Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines.
- amine dispersants include those described in, for example, U.S. Patent Nos. 3,275,554 , 3,438,757 , 3,454,555 and 3,565,804 .
- Suitable ashless dispersants may further include "Mannich dispersants," which are reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). Examples of such dispersants include those described in, for example, U.S. Patent Nos. 3,036,003 , 3,586,629 , 3,591,598 and 3,980,569 .
- Suitable ashless dispersants may also be post-treated ashless dispersants such as post-treated succinimides, e.g., post-treatment processes involving borate or ethylene carbonate as disclosed in, for example, U.S. Patent Nos. 4,612,132 and 4,746,446 ; and the like as well as other post-treatment processes.
- the carbonate-treated alkenyl succinimide is a polybutene succinimide derived from polybutenes having a molecular weight of about 450 to about 3000, preferably from about 900 to about 2500, more preferably from about 1300 to about 2400, and most preferably from about 2000 to about 2400, as well as mixtures of these molecular weights.
- it is prepared by reacting, under reactive conditions, a mixture of a polybutene succinic acid derivative, an unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin, and a polyamine, such as disclosed in U.S. Patent No. 5,716,912 , the contents of which are incorporated herein by reference.
- Metal-containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
- Detergents generally comprise a polar head with a long hydrophobic tail.
- the polar head comprises a metal salt of an acidic organic compound.
- the salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to about 80.
- TBN total base number
- a large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).
- the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle.
- a metal base e.g., carbonate
- Such overbased detergents may have a TBN of about 50 or greater, or a TBN of about 100 or greater, or a TBN of about 200 or greater, or a TBN of from about 250 to about 450 or more.
- Representative examples of other metal detergents that can be included in the marine diesel cylinder lubricating oil composition of the present invention include phenates, aliphatic sulfonates, alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a TBN of equal to or less than 250, alkali metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid, phosphonates, and phosphinates.
- the salts of the alkyl-substituted hydroxyaromatic carboxylic acid can be as described above.
- Overbased metal detergents are generally produced by carbonating a mixture of hydrocarbons, detergent acid, for example: sulfonic acid, carboxylate etc., metal oxide or hydroxides (for example calcium oxide or calcium hydroxide) and promoters such as xylene, methanol and water.
- detergent acid for example: sulfonic acid, carboxylate etc.
- metal oxide or hydroxides for example calcium oxide or calcium hydroxide
- promoters such as xylene, methanol and water.
- the calcium oxide or hydroxide reacts with the gaseous carbon dioxide to form calcium carbonate.
- the sulfonic acid is neutralized with an excess of CaO or Ca(OH) 2 , to form the sulfonate.
- Overbased detergents may be low overbased, e.g., an overbased salt having a BN below about 100.
- the BN of a low overbased salt may be from about 5 to about 50.
- the BN of a low overbased salt may be from about 10 to about 30.
- the BN of a low overbased salt may be from about 15 to about 20.
- Overbased detergents may be medium overbased, e.g., an overbased salt having a BN from about 100 to about 250.
- the BN of a medium overbased salt may be from about 100 to about 200.
- the BN of a medium overbased salt may be from about 125 to about 175.
- Overbased detergents may be high overbased, e.g., an overbased salt having a BN above 250.
- the BN of a high overbased salt may be from about 250 to about 550.
- rust inhibitors include, but are not limited to, nonionic polyoxyalkylene agents, e.g., polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acids; metal soaps; fatty acid amine salts; metal salts of heavy sulfonic acid; partial carboxylic acid ester of polyhydric alcohol; phosphoric esters; (short-chain) alkenyl succinic acids; partial esters thereof and nitrogen-containing derivatives thereof; synthetic alkarylsulfonates, e.g., metal dinonylnaphthalene sulfon
- friction modifiers include, but are not limited to, alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No.
- friction modifiers obtained from a reaction product of a C 4 to C 75 , preferably a C 6 to C 24 , and most preferably a C 6 to C 20 , fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an alkanolamine, e.g., a mono- or dialkanolamine, and the like and mixtures thereof.
- antiwear agents include, but are not limited to, zinc dialkyldithiophosphates and zinc diaryldithiophosphates, e.g., those described in an article by Born et al. entitled “Relationship between Chemical Structure and Effectiveness of Some Metallic Dialkyl- and Diaryl-dithiophosphates in Different Lubricated Mechanisms", appearing in Lubrication Science 4-2 January 1992 , see for example pages 97-100; aryl phosphates and phosphites, sulfur-containing esters, phosphosulfur compounds, metal or ash-free dithiocarbamates, xanthates, alkyl sulfides and the like and mixtures thereof.
- antifoaming agents include, but are not limited to, polymers of alkyl methacrylate; polymers of dimethylsilicone and the like and mixtures thereof.
- a pour point depressant examples include, but are not limited to, polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates of a chlorinated paraffin with naphthalene and combinations thereof.
- a pour point depressant comprises an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, polyalkyl styrene and the like and combinations thereof.
- the amount of the pour point depressant may vary from about 0.01 wt. % to about 10 wt. %.
- demulsifier examples include, but are not limited to, anionic surfactants (e.g., alkyl-naphthalene sulfonates, alkyl benzene sulfonates and the like), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids, polyoxyethylene sorbitan ester and the like and combinations thereof.
- the amount of the demulsifier may vary from about 0.01 wt. % to about 10 wt. %.
- Examples of a corrosion inhibitor include, but are not limited to, half esters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines, sarcosines and the like and combinations thereof.
- the amount of the corrosion inhibitor may vary from about 0.01 wt. % to about 0.5 wt. %.
- an extreme pressure agent examples include, but are not limited to, sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acid, fatty acid ester and alphaolefin, functionally-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpene and acyclic olefins, and polysulfide olefin products, amine salts of
- each of the foregoing additives when used, is used at a functionally effective amount to impart the desired properties to the lubricant.
- a functionally effective amount of this friction modifier would be an amount sufficient to impart the desired friction modifying characteristics to the lubricant.
- the concentration of each of these additives, when used ranges from about 0.001% to about 20% by weight, and in one embodiment about 0.01% to about 10% by weight based on the total weight of the lubricating oil composition.
- the foregoing marine diesel cylinder lubricating oil composition additives may be provided as an additive package or concentrate in which the additives are incorporated into a substantially inert, normally liquid organic diluent as described above.
- the additive package will typically contain one or more of the various additives, referred to above, in the desired amounts and ratios to facilitate direct combination with the requisite amount of the oil of lubricating viscosity.
- the marine diesel cylinder lubricating oil composition of the present invention is substantially free or free of any dispersants and/or zinc compounds, e.g., zinc dithiophosphates.
- the term "substantially free” as used herein means relatively low levels, if any, of each of the dispersants and/or zinc compounds, e.g., less than about 0.5 wt. % of each of the dispersants and/or zinc compounds in the marine diesel cylinder lubricating oil composition. In another embodiment, the term “substantially free” is less than about 0.1 wt. % of each of the dispersants and/or zinc compounds in the marine diesel cylinder lubricating oil composition. In another embodiment, the term “substantially free” is less than about 0.01 wt. % of each of the dispersants and/or zinc compounds in the marine diesel cylinder lubricating oil composition.
- total TPP concentration of total TPP and its unsulfurized metal salt in the marine diesel cylinder lubricating oil composition of the present invention
- total TPP concentration of total TPP and its unsulfurized metal salt in the marine diesel cylinder lubricating oil composition of the present invention
- total residual TPP concentration of total TPP and its unsulfurized metal salt in the marine diesel cylinder lubricating oil composition of the present invention
- HPLC High Performance Liquid Chromatography
- the HPLC system used in the HPLC method included a HPLC pump, a thermostatted HPLC column compartment, HPLC fluorescence detector, and PC-based chromatography data acquisition system.
- the particular system described is based on an Agilent 1200 HPLC with ChemStation software.
- the HPLC column was a Phenomenex Luna C8(2) 150 x 4.6mm 5 ⁇ m 100 ⁇ , P/N 00F4249E0.
- the resulting chromatograph typically contains several peaks. Peaks due to the free unsulfurized alkylhydroxyaromatic compound (i.e., TPP) typically elute together at early retention times; whereas peaks due to sulfurized alkylhydroxyaromatic compounds typically elute at longer retention times.
- TPP free unsulfurized alkylhydroxyaromatic compound
- sulfurized alkylhydroxyaromatic compounds typically elute at longer retention times.
- the area of the single largest peak of the free unsulfurized alkylhydroxyaromatic compound and its unsulfurized metal salt was measured, and then that area was used to determine the concentration of the total free unsulfurized alkylhydroxyaromatic compound and its unsulfurized metal salt species. The assumption is that the speciation of alkylhydroxyaromatic compounds does not change; if something does change the speciation of the alkylhydroxyaromatic compounds, then recalibration is necessary.
- the area of the chosen peak is compared to a calibration curve to arrive at the wt-% of free alkylphenol and free unsulfurized salts of alkylphenols.
- the calibration curve was developed using the same peak in the chromatograph obtained for the free unsulfurized alkylhydroxyaromatic compound used to make the phenate product.
- the Komatsu Hot Tube test is a lubrication industry bench test that measures the detergency and thermal and oxidative stability of a lubricating oil. Detergency and thermal and oxidative stability are performance areas that are generally accepted in the industry as being essential to satisfactory overall performance of a lubricating oil.
- a specified amount of test oil is pumped upwards through a glass tube that is placed inside an oven set at a certain temperature. Air is introduced in the oil stream before the oil enters the glass tube, and flows upward with the oil. Evaluations of the marine diesel cylinder lubricating oils were conducted at temperatures between 300-330 degrees Celsius.
- the test result is determined by comparing the amount of lacquer deposited on the glass test tube to a rating scale ranging from 1.0 (very black) to 10.0 (perfectly clean). The result is reported in multiples of 0.5.
- Blockage is a deposition in which case the lacquer is very thick and most of the glass test tube is blocked, preventing normal oil and air flow through the test tube. Although blocking can be considered a result inferior to a 1.0 rating, its occurrence can be greatly influenced by blocking of other test tubes that are simultaneously tested in the same test run.
- Chevron 600N RLOP Group II-based lubricating oil was Chevron 600N RLOP basestock, available from Chevron Products Company (San Ramon, CA.).
- ExxonMobil CORE® 2500BS Group I-based lubricating oil was ExxonMobil CORE® 2500BS basestock, available from ExxonMobil (Irving, TX.).
- Detergent A An oil concentrate of a neutral (non-overbased) calcium alkylhydroxybenzoate additive, having an alkyl substituent derived from C 20 to C 28 linear olefins, prepared according to the method described in Example 1 of US Patent Application 2007/0027043 , but without the subsequent overbasing step.
- This additive concentrate contained 2.17 wt. % Ca and about 43.0 wt. % diluent oil, and had a TBN of 61. On an active basis, the TBN of this additive (absent diluent oil) is 107.
- Detergent B An oil concentrate of an overbased sulfurized calcium phenate derived from propylene tetramer. This additive contained 9.6 wt. % Ca, and about 31.4 wt. % diluent oil, and had a TBN of 260.. Detergent B is believed to have a total TPP content, i.e., TPP and its unsulfurized metal salt, of from about 5 to 7 wt.%, based on the weight of the detergent as manufactured.
- Detergent C An oil concentrate of an unsulfurized, non-overbased alkylhydroxybenzoate-containing, phenol-distilled additive, having an alkyl substituent derived from about 50 wt. % C 20 to C 28 linear olefins and 50 wt. % branched hydrocarbyl radical propylene tetramer, prepared according to the method described in Example 1 of US Patent Application 2004/0235686 .
- This additive contained 5.00 wt. % Ca, and about 33.0 wt. % diluent oil, and had a TBN of 140. On an active basis, the TBN of this additive (absent diluent oil) is 210.
- Detergent C is believed to have a total TPP content, i.e., TPP and its unsulfurized metal salt, of from about 2 to 3 wt.%, based on the weight of the detergent as manufactured.
- Detergent D An oil concentrate of an overbased calcium alkylhydroxybenzoate additive, having an alkyl substituent derived from C 20 to C 28 linear olefins, prepared according to the method described in Example 1 of US Patent Application 2007/0027043 .
- This additive contained 5.35 wt. % Ca, and about 35.0 wt. % diluent oil, and had a TBN of 150. On an active basis, the TBN of this additive (absent diluent oil) is 230.
- Detergent E An oil concentrate of an overbased calcium alkylhydroxybenzoate additive, having an alkyl substituent derived from C 20 to C 28 linear olefins, prepared according to the method described in Example 1 of US Patent Application 2007/0027043 .
- This additive contained 12.5 wt. % Ca, and about 33.0 wt. % diluent oil, and had a TBN of 350. On an active basis, the TBN of this additive (absent diluent oil) is 522.
- Detergent F An oil concentrate of an overbased calcium alkyltoluene sulfonate detergent; wherein the alkyl group is derived from C 20 to C 24 linear alpha olefins.
- This additive concentrate contained 16.1 wt. % Ca, and about 38.7 wt. % diluent oil, and had a TBN of 420. On an active basis, the TBN of this additive (absent diluent oil) is 685.
- Detergent G An oil concentrate of an overbased calcium alkylhydroxybenzoate additive, having an alkyl substituent derived from C 14 to C 18 linear alpha olefins. This additive contained 6.25 wt. % Ca, and about 41.0 wt. % diluent oil, and had a TBN of 175. On an active basis, the TBN of this additive (absent diluent oil) is 296.
- the marine diesel engine lubricating oil compositions of Examples 1-3 and Comparative Examples A-J were prepared as set forth below in Table 1.
- Each marine diesel engine lubricating oil composition of Example 1 and Comparative Examples A-J were a SAE 40 viscosity grade oil, having a kinematic viscosity of about 14.5 cSt @100°C, and a TBN of 40 mg KOH/g.
- Example 2 was a SAE 50 viscosity oil, having a kinematic viscosity of about 18.7 cSt @100°C and a TBN of about 70 mgKOH/g.
- Example 3 was a SAE 50 viscosity oil, having a kinematic viscosity of about 18.9 cSt @100°C and a TBN of about 20 mgKOH/g.
- the marine diesel engine lubricating oil compositions of Examples 1-3 and Comparative Examples A-J were formulated using a major amount of Group II basestock and a minor amount of a Group I basestock, a detergent composition as defined in Table 1, and 0.04 wt. % foam inhibitor. Comparative Example D further comprised 0.57 wt.
- PIBSA polyisobutylene succinic anhydride
- HPA heavy polyamine
- DETA diethylene triamine
- Examples 1-3 which contain the inventive detergent composition, exhibited surprisingly improved detergency performance over the marine diesel cylinder lubricating oil compositions of Comparative Examples A-J. This is illustrated by higher KHT values which were sustained over higher temperature ranges, indicating that the marine diesel cylinder lubricating oil compositions of Examples 1-3 exhibit excellent detergency and thermal stability in the hot tube test in that they produce little lubricating oil oxidation or degradation product to defile the tube.
- Examples 1-3 are substantially free of TPP and its unsulfurized metal salt.
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Claims (13)
- Composition d'huile lubrifiante pour cylindre diesel marin comprenant(a) une quantité majeure d'une ou des plusieurs huiles de base du Groupe II, et(b) une composition détergente comprenantdans laquelle la composition d'huile lubrifiante pour cylindre diesel marin a un TBN de 5 à 120 ; dans laquelle l'un ou les plusieurs acides sulfoniques alkylaromatiques hautement surbasiques ou leurs sels ont un TBN supérieur à 250 ; et dans laquelle le TBN est mesuré conformément à la norme ASTM n° D2896 ou à un procédé équivalent.(i) de 0,1 à 35% en poids sur une base en actifs d'un ou des plusieurs sels de métal alcalinoterreux d'un acide carboxylique hydroxyaromatique à substitution alkyle ayant un indice de basicité (TBN) supérieur à 250, par rapport au poids total de la composition d'huile lubrifiante pour cylindre diesel marin; et(ii) de 0,1 à 34 % en poids sur une base en actifs d'un ou des plusieurs acides sulfoniques alkylaromatiques hautement surbasiques ou leurs sels, par rapport au poids total de la composition d'huile lubrifiante pour cylindre diesel marin ; dans laquelle le reste aromatique des acides sulfoniques alkylaromatiques ou de leurs sels ne contient pas de groupes hydroxyle ;
- La composition d'huile lubrifiante pour cylindre diesel marin selon la revendication 1 ayant un TBN de 20 à 100.
- La composition d'huile lubrifiante pour cylindre diesel marin selon la revendication 1 ayant un TBN de 10 à 40.
- La composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 3, qui contient moins de 1,5% en poids de tétra-propénylphénol (TPP) et de son sel non sulfuré.
- La composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 4, dans laquelle l'un ou les plusieurs sels de métal alcalino-terreux d'un acide carboxylique hydroxyaromatique à substitution alkyle sont un ou plusieurs sels de calcium d'un acide carboxylique hydroxyaromatique à substitution alkyle.
- La composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 5, dans laquelle la fraction à substitution alkyle du sel de métal alcalino-terreux d'un acide carboxylique hydroxyaromatique à substitution alkyle est un groupe alkyle en C10 à C40.
- La composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 5, dans laquelle l'un ou les plusieurs sels de métal alcalinoterreux d'un acide carboxylique hydroxyaromatique à substitution alkyle ont un TBN supérieur à 250 et jusqu'à 800.
- La composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 7, dans laquelle l'un ou les plusieurs acides sulfoniques alkylaromatiques hautement surbasiques ou leurs sels sont un ou plusieurs sulfonates de métal alcalino-terreux alkylaromatiques hautement surbasiques.
- La composition d'huile lubrifiante pour cylindre diesel marin une quelconque des revendications 1 à 7, dans laquelle l'un ou les plusieurs acides sulfoniques alkylaromatiques hautement surbasiques ou leurs sels sont un ou plusieurs sulfonates de calcium alkylaromatiques hautement surbasiques.
- La composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 9, comprenant en outre un ou plusieurs additifs de composition d'huile lubrifiante pour cylindre diesel marin choisis parmi le groupe constitué en un antioxydant, un dispersant sans cendres, un détergent, un inhibiteur de rouille, un agent anti-trouble, un agent de démulsification, un agent de désactivation des métaux, un modificateur de friction, un dépresseur du point d'écoulement, un agent antimousse, un co-solvant, un inhibiteur de corrosion, des colorants, un agent de pression extrême et leurs mélanges.
- La composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 10, qui comprend moins de 0,5% en poids de quelconques dispersants et/ou composés de zinc.
- Procédé pour lubrifier un moteur marin diesel à crosse à deux temps, dans lequel le procédé comprend opérer le moteur avec une composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 11.
- Utilisation d'une composition d'huile lubrifiante pour cylindre diesel marin selon une quelconque des revendications 1 à 11 pour améliorer la détergence à température élevée et la stabilité thermique dans un moteur marin diesel à crosse à deux temps.
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---|---|---|---|---|
EP0725129B1 (fr) * | 1995-02-01 | 2001-12-12 | The Lubrizol Corporation | Composition lubrificante à faible teneur en cendre |
JP4011815B2 (ja) * | 2000-02-14 | 2007-11-21 | シェブロンジャパン株式会社 | 二サイクルクロスヘッドディーゼル内燃機関用潤滑油組成物および該潤滑油組成物用添加剤組成物 |
JP2004083746A (ja) * | 2002-08-27 | 2004-03-18 | Nippon Oil Corp | 内燃機関用潤滑油組成物 |
US8188020B2 (en) * | 2003-12-22 | 2012-05-29 | Chevron Oronite S.A. | Lubricating oil composition containing an alkali metal detergent |
US8618029B2 (en) | 2003-12-22 | 2013-12-31 | Chevron Oronite S.A. | Overbased detergents for lubricating oil applications |
CN102365353A (zh) * | 2009-04-07 | 2012-02-29 | 英菲诺姆国际有限公司 | 船舶发动机润滑 |
US8383562B2 (en) * | 2009-09-29 | 2013-02-26 | Chevron Oronite Technology B.V. | System oil formulation for marine two-stroke engines |
US8580717B2 (en) * | 2009-11-24 | 2013-11-12 | Chevron Oronite Company Llc | Process for making an overbased, sulfurized salt of an alkylated hydroxyaromatic compound |
JP5483329B2 (ja) * | 2009-12-24 | 2014-05-07 | Jx日鉱日石エネルギー株式会社 | クロスヘッド型ディーゼル機関用シリンダー潤滑油組成物 |
US8476460B2 (en) * | 2011-01-21 | 2013-07-02 | Chevron Oronite Company Llc | Process for preparation of low molecular weight molybdenum succinimide complexes |
JP5796869B2 (ja) * | 2011-09-29 | 2015-10-21 | シェブロンジャパン株式会社 | 潤滑油組成物 |
US9206374B2 (en) * | 2011-12-16 | 2015-12-08 | Chevron Oronite Sas | Trunk piston engine lubricating oil compositions |
JP5773365B2 (ja) * | 2011-12-27 | 2015-09-02 | シェブロンジャパン株式会社 | 省燃費性の内燃機関用潤滑油組成物 |
US9434906B2 (en) * | 2013-03-25 | 2016-09-06 | Chevron Oronite Company, Llc | Marine diesel engine lubricating oil compositions |
JP6509239B2 (ja) * | 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. | 船舶用ディーゼルシリンダー潤滑油組成物 |
-
2015
- 2015-11-06 WO PCT/EP2015/075988 patent/WO2016071518A1/fr active Application Filing
- 2015-11-06 US US14/934,541 patent/US20170107443A1/en not_active Abandoned
- 2015-11-06 CN CN201580060225.9A patent/CN107075404A/zh active Pending
- 2015-11-06 SG SG11201703714XA patent/SG11201703714XA/en unknown
- 2015-11-06 JP JP2017524037A patent/JP6810033B2/ja active Active
- 2015-11-06 EP EP15790598.5A patent/EP3215591B1/fr active Active
- 2015-11-06 KR KR1020177013778A patent/KR102613191B1/ko active IP Right Grant
- 2015-11-06 CN CN202410331873.4A patent/CN118222347A/zh active Pending
-
2022
- 2022-03-08 US US17/689,839 patent/US20220403283A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CN107075404A (zh) | 2017-08-18 |
JP6810033B2 (ja) | 2021-01-06 |
US20170107443A1 (en) | 2017-04-20 |
KR102613191B1 (ko) | 2023-12-14 |
US20220403283A1 (en) | 2022-12-22 |
WO2016071518A1 (fr) | 2016-05-12 |
JP2017533330A (ja) | 2017-11-09 |
CN118222347A (zh) | 2024-06-21 |
KR20170082544A (ko) | 2017-07-14 |
EP3215591A1 (fr) | 2017-09-13 |
SG11201703714XA (en) | 2017-06-29 |
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