EP2021440B1 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
- Publication number
- EP2021440B1 EP2021440B1 EP07728774.6A EP07728774A EP2021440B1 EP 2021440 B1 EP2021440 B1 EP 2021440B1 EP 07728774 A EP07728774 A EP 07728774A EP 2021440 B1 EP2021440 B1 EP 2021440B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating oil
- oil composition
- turbine
- lubricating
- groups
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 108
- 239000010687 lubricating oil Substances 0.000 title claims description 88
- 239000002199 base oil Substances 0.000 claims description 53
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 30
- 238000012360 testing method Methods 0.000 claims description 24
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims description 22
- 230000001050 lubricating effect Effects 0.000 claims description 19
- 239000004922 lacquer Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229920013639 polyalphaolefin Polymers 0.000 claims description 7
- 241000282461 Canis lupus Species 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical class C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 5
- 125000004981 cycloalkylmethyl group Chemical group 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 239000005069 Extreme pressure additive Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- -1 alkyl diphenylamines Chemical class 0.000 description 40
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 24
- 239000010802 sludge Substances 0.000 description 15
- 238000009472 formulation Methods 0.000 description 12
- 229940035422 diphenylamine Drugs 0.000 description 11
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 11
- 239000000314 lubricant Substances 0.000 description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010723 turbine oil Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000007866 anti-wear additive Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 150000003582 thiophosphoric acids Chemical class 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GLEAJEPGOSMZLQ-UHFFFAOYSA-N 1-octyl-n-(4-octylphenyl)naphthalen-2-amine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(C=CC=C2)C2=C1CCCCCCCC GLEAJEPGOSMZLQ-UHFFFAOYSA-N 0.000 description 1
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical compound SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 description 1
- XVEYHYHXRYVWJW-UHFFFAOYSA-N 2-ethyl-n-(2-ethyl-4-nonylphenyl)-4-nonylaniline Chemical compound CCC1=CC(CCCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCCC)C=C1CC XVEYHYHXRYVWJW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010727 cylinder oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 1
- LCHMEXFHRGKPAB-UHFFFAOYSA-N n-(2,4-diethylphenyl)-2,4-diethylaniline Chemical compound CCC1=CC(CC)=CC=C1NC1=CC=C(CC)C=C1CC LCHMEXFHRGKPAB-UHFFFAOYSA-N 0.000 description 1
- BQLZCNHPJNMDIO-UHFFFAOYSA-N n-(4-octylphenyl)naphthalen-1-amine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=CC2=CC=CC=C12 BQLZCNHPJNMDIO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SRWPBFLLYKIZTL-UHFFFAOYSA-N n-hexyl-n-phenylnaphthalen-2-amine Chemical compound C=1C=C2C=CC=CC2=CC=1N(CCCCCC)C1=CC=CC=C1 SRWPBFLLYKIZTL-UHFFFAOYSA-N 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- SNWVRVDHQRBBFG-UHFFFAOYSA-N n-phenyl-n-(2,4,4-trimethylpentan-2-yl)naphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(C(C)(C)CC(C)(C)C)C1=CC=CC=C1 SNWVRVDHQRBBFG-UHFFFAOYSA-N 0.000 description 1
- MHJCZOMOUCUAOI-UHFFFAOYSA-N n-tert-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C(C)(C)C)C1=CC=CC=C1 MHJCZOMOUCUAOI-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010736 steam turbine oil Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
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- 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
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
- C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
- C10M2205/223—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts used as base material
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- C10M2207/2805—Esters used as base material
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- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
- C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
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- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl amines
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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- 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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- 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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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/12—Gas-turbines
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/135—Steam engines or turbines
Definitions
- the present invention relates to lubricating oil compositions, more specifically to lubricating oil compositions for lubricating turbines and in particular, to lubricating oil compositions for lubricating a combination of a steam turbine and a gas turbine.
- a difficulty of lubricating a combined cycle resides in the large variety of different components which must be lubricated, i.e. bearings (both journal and thrust), gears, hydraulic control systems, flexible couplings and oil shaft seals. Although each component could be lubricated per se , it is advantageous to have a single, common lubricating system containing a single, common lubricant for all components.
- the lubricating oil composition for use in the common system has to meet a rather outstanding combination of requirements in order to satisfactorily lubricate each component. These requirements comprise the rather severe thermal and oxidative stability requirements and stringent foaming levels for the gas turbine part, whereas the steam turbine part requires the oil to have good water shedding properties and excellent corrosion resistance.
- High temperature oxidative stability means that the lubricating oil composition has a low tendency to form sludge, a low increase in viscosity and a low increase in total acid number at high temperature. Desirable characteristics are a viscosity increase of at most 20 %, a total acid number increase of at most 3.0 mg KOH/g and a sludge content of less than 300 mg/100 ml after having been subjected to the oxidation stability test DIN 51394 performed according to the high temperature modifications set out in the General Electric specifications GEK 32568 C and GEK 101941, preferably less than 250 ml/g, more preferably less than 200 ml/g, most preferably less than 150 ml/g. In establishing the amount of sludge produced, the sludge must be removed carefully from all the equipment used in the test. The sludge is separated from the oil by filtration.
- a lubricating oil composition for use in combined cycle equipment must further have a certain viscosity index, pour point, filterability and anti-wear performance, while the composition should provide adequate lubrication over many years.
- the typical lifetime of a turbine oil can be approximately 5 to 10 years or more.
- EP-A-0696636 describes a lubricating oil composition for use in internal combustion engines which comprises a combination of (A) a lubricating base oil, (B) one or more alkyl diphenylamines and/or one or more phenyl- ⁇ -naphthylamines and (C) oxymolybdenum sulfide dithiocarbamate and/or oxymolybdenum sulfide organophosphorodithioate.
- EP-A-0696636 either a single alkyl diphenylamine or a single phenyl- ⁇ -naphthylamine is used.
- Oxymolybdenum sulfide organophosphorodithioate is present in only one of the examples according to the teaching.
- EP-A-0696636 is not concerned with reducing lacquer formation in turbines and does not disclose or teach any lubricating oil compositions for this purpose.
- GB-B-0990097 discloses a lubricating oil composition for use in aviation gas turbine engines which comprises blend of synthetic base oils and an aliphatic thiophosphate or a polymerised or sulphurised product thereof. Said composition may optionally comprise one or more anti-oxidant additives.
- DE-A-1594405 describes lubricating oil compositions for steam turbines comprising mineral oil and (a) an aliphatic polycarboxylic acid containing at least 12 carbon atoms, (b) an alkylphenol, (c) an aromatic amine, and (d) a dialkyldithiophosphate.
- DE-A-1594405 states that aromatic amines normally have a tendency to form sludge and have unsatisfactory light stability, whilst the lubricating oil compositions in accordance with DE-A-1594405 have better stability.
- the aromatic amine (c) in DE-A-1594405 may be a secondary aromatic amine such as diphenylamine, phenyl-alpha- or -beta-naphthylamine and alkyl substituted analogues such as p,p'-dioctyldiphenylamine.
- US 3 923 672 discloses a lubricating composition particularly suitable for use in steam turbines or gas turbines.
- FR 2 832 417 discloses a lubricating composition comprising a mixture of esters as a base oil, a specific diphenylamine and a specific phenyl-alpha-naphthylamine. No bright stock oil is mentioned.
- US 3 844 963 discloses a lubricating composition comprising a base oil and a dithiophosphoric acid derivative. No bright stock oil is mentioned.
- US 2003/096713 discloses a lubricating composition
- a lubricating composition comprising a base oil, one or more antioxidants and from 0.01 wt.% to 3 wt.% of at least one dispersant or detergent, wherein the total amount of antioxidant is at least 2 wt.%. No bright stock oil is mentioned.
- US 5 726 135 discloses a lubricating composition for aircraft and turbo engine end-use application comprising a synthetic base oil and an alkylated or alkarylated dithiocarbamate, wherein the composition is absolutely free of phosphorus, metals, metal salts, and detergent/diapersant. No bright stock oil is mentioned.
- US 5 520 830 discloses a method of reducing the level of oxidation of a lubricant, which comprises incorporating soluble copper in the lubricant in an amount above 1200 ppm. No bright stock oil is mentioned.
- WO 98/02510 discloses a lubricating composition comprising an alkyl-substituted naphthalene and an ester. No bright stock oil is mentioned.
- WO-A-99/43770 discloses a lubricating oil composition for use in a combined cycle which comprises a hydrocarbon lubricant base oil in combination with (a) a phenyl-naphthylamine, (b) a thiophosphate and (c) a diphenyl amine.
- a combination of non-substituted phenyl-alpha-naphthylamine and an amine salt of a dialkyldithiophosphate are used in conjunction with additional amine antioxidant.
- WO-A-99/43770 discloses a lubricating oil composition which exhibits an especially low tendency to form sludge at high temperatures. However, WO-A-99/43770 does not discuss the reducing lacquer formation in combined cycle equipment.
- a lubricating oil composition comprising a specific combination of components, which composition not only meets the requirements for use in a combined cycle as disclosed in WO-A-99/43770 but which lubricating oil composition also exhibits low lacquer formation.
- the present invention provides a lubricating oil composition according to claim 1.
- the one or more substituted phenyl-naphthylamines (a) which are used in the present invention, can be used as such or in the form of a salt.
- Examples of such substituted phenyl-naphthylamines are substituted phenyl-alpha-naphthylamines and substituted phenyl-beta-naphthylamines.
- the one or more substituted phenyl-naphthylamines are preferably substituted phenyl-alpha-naphthylamines.
- Preferred substituted phenyl-naphthylamines are alkylated phenyl-alpha-naphthylamines and/or alkylated phenyl-beta-naphthylamines. More preferably, said substituted phenyl-naphthylamines are mono-alkylated phenyl-alpha-naphthylamines and/or mono-alkylated phenyl-beta-naphthylamines.
- Particularly preferred mono-alkylated phenyl-alpha-naphthylamines and mono-alkylated phenyl-beta-naphthylamines are those wherein the alkyl substituents are straight chain or branched alkyl groups having in the range of from 1 to 18 carbon atoms.
- substituted phenyl-naphthylamines examples include octylphenyl-beta-naphthylamine, t-octylphenyl-alpha-naphthylamine, p-octylphenyl-alpha-naphthylamine, 4-octylphenyl-1-octyl-beta-naphthylamine, n-t-dodecylphenyl-1-naphthylamine, N-hexylphenyl-2-naphthylamine.
- a particularly preferred substituted phenyl-alpha-naphthylamine is a monooctylated phenyl alpha-naphthylamine.
- Substituted phenyl-naphthylamines as commercially available can be used in the present invention.
- one or more thiophosphates are used, preferably one or more ashless thiophosphates. Ashless thiophosphates are known in the art. These compounds are metal-free organic compounds.
- the one or more ashless thiophosphates may be esters and/or salts of thiophosphoric acids, substituted thiophosphoric acids.
- the ashless thiophosphates are substituted by one or more hydrocarbyl groups which hydrocarbyl groups can optionally contain an acid, a hydroxy and/or an ester group.
- the hydrocarbyl moiety preferably is an alkyl containing up to 12 carbon atoms.
- the hydrocarbyl substituted thiophosphate preferably contains 2 or 3 hydrocarbyl groups, or is a mixture of thiophosphates containing 2 and 3 hydrocarbyl groups.
- the ashless thiophosphates can contain any number of sulphur atoms directly linked to the phosphorus atom.
- the thiophosphates are monothiophosphates and/or dithiophosphates.
- ashless thiophosphates which may be conveniently used in the lubricating oil composition of the present invention are described in EP-A-0375324 , US-A-5922657 , US-A-4333841 and US-A-5093016 and may be conveniently made according to the methods described therein.
- the one or more ashless thiophosphates are preferably compounds according to formula (I) wherein R 1 and R 2 are each, independently, selected from hydrogen, branched or straight chain C 1 to C 18 alkyl groups which may be interrupted by 1 or 2 oxygen atoms, C 5 to C 12 cycloalkyl groups, C 5 to C 9 cycloalkylmethyl groups, C 9 to C 10 bicycloalkylmethyl groups, C 9 to C 10 tricycloalkylmethyl groups, phenyl or C 7 to C 24 alkylphenyl groups or R 1 and R 2 together may be a C 2 to C 12 alkylene group which may be interrupted by 1 or 2 oxygen atoms, R 3 and R 4 are each, independently, selected from hydrogen and branched or straight chain C 1 to C 8 alkyl groups which may be interrupted by 1 or 2 oxygen atoms, n is an integer from 1 to 5 and X is selected from -OH, -OR 5 wherein R 5 is selected from branched or straight chain alkyl groups
- R 1 and R 2 are each, independently, selected from hydrogen, branched or straight chain C 3 to C 18 alkyl groups, C 5 to C 12 cycloalkyl groups, C 5 to C 9 cycloalkylmethyl groups, C 9 to C 10 bicycloalkylmethyl groups, C 9 to C 10 tricycloalkylmethyl groups, phenyl or C 7 to C 24 alkylphenyl groups or R 1 and R 2 together may be a C 2 to C 12 alkylene group which may be interrupted by 1 or 2 oxygen atoms.
- R 1 and R 2 are each, independently, selected from hydrogen, branched or straight chain C 3 to C 18 alkyl groups selected from propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethylhexyl and 1-methylund
- R 3 and R 4 groups in each repeating unit may be the same or different from R 3 and R 4 groups in other repeating units.
- R 3 and R 4 are each selected, independently, from hydrogen, methyl and ethyl.
- the one or more ashless thiophosphates are preferably compounds according to formula (II) wherein R 8 and R 9 are each, independently, selected from hydrogen, branched or straight chain C 1 to C 18 alkyl groups which may be interrupted by 1 or 2 oxygen atoms, C 5 to C 12 cycloalkyl groups, C 5 to C 9 cycloalkylmethyl groups, C 9 to C 10 bicycloalkylmethyl groups, C 9 to C 10 tricycloalkylmethyl groups, phenyl or C 7 to C 24 alkylphenyl groups or R 8 and R 9 together may be a C 2 to C 12 alkylene group which may be interrupted by 1 or 2 oxygen atoms, R 10 is selected from hydrogen and branched or straight chain C 1 to C 8 alkyl groups which may be interrupted by 1 or 2 oxygen atoms.
- R 8 and R 9 are each, independently, selected from hydrogen, branched or straight chain C 1 to C 18 alkyl groups which may be interrupted by 1 or 2 oxygen atoms, C 5
- R 8 and R 9 are each, independently, selected from hydrogen, branched or straight chain C 3 to C 18 alkyl groups, C 5 to C 12 cycloalkyl groups, C 5 to C 9 cycloalkylmethyl groups, C 9 to C 10 bicycloalkylmethyl groups, C 9 to C 10 tricycloalkylmethyl groups, phenyl or C 7 to C 24 alkylphenyl groups or R 8 and R 9 together may be a C 2 to C 12 alkylene group which may be interrupted by 1 or 2 oxygen atoms.
- R 8 and R 9 are each, independently, selected from hydrogen, branched or straight chain C 3 to C 18 alkyl groups selected from propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethylhexyl and 1-methylund
- R 10 is selected from hydrogen, methyl and ethyl.
- ashless thiophosphates examples include those available from Ciba Specialty Chemicals under the trade designations "IRGALUBE L-63" and “IRGALUBE 353" and that available from Lubrizol under the trade designation "LZ 5125".
- the amount of the additives (a) and (b) present in the lubricating oil composition of the present invention depends on the specific compounds used therein.
- the one or more substituted phenyl-naphthylamines (a) are present in the lubricating oil composition of the present invention in a total amount in the range of from 0.01 to 3.0 wt. %, preferably in the range of from 0.01 to 1.0 wt. %, based on the total weight of the lubricating oil composition.
- the one or more ashless thiophosphates are preferably present in the lubricating oil composition of the present invention in a total amount in the range of from 0.01 to 1.0 wt. %, more preferably in the range of from 0.01 to 0.1 wt. %, based on the total weight of the lubricating oil composition.
- the lubricating oil base oil in the lubricating oil composition of the present invention may be selected from mineral and/or synthetic lubricant base oils.
- Said lubricating oil base oil is preferably present in an amount of at least 85 wt. %, more preferably at least 90 wt. %, based on the total weight of the lubricating oil composition.
- Mineral lubricant base oils that may be conveniently used include liquid petroleum oils and solvent treated or acid treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrocracking and hydrofinishing processes and/or dewaxing.
- Naphthenic base oils have low viscosity index (VI) (generally 40-80) and a low pour point.
- Such base oils are produced from feedstocks rich in naphthenes and low in wax content and are used mainly for lubricants in which colour and colour stability are important, and VI and oxidation stability are of secondary importance.
- Paraffinic base oils have higher VI (generally >95) and a high pour point. Said base oils are produced from feedstocks rich in paraffins, and are used for lubricants in which VI and oxidation stability are important.
- Fischer-Tropsch derived base oils may be conveniently used as the lubricating oil base oil in the lubricating oil composition of the present invention, for example, the Fischer-Tropsch derived base oils disclosed in EP-A-776959 , EP-A-668342 , WO-A-97/21788 , WO-00/15736 , WO-00/14188 , WO-00/14187 , WO-00/14183 , WO-00/14179 , WO-00/08115 , WO-99/41332 , EP-1029029 , WO-01/18156 and WO-01/57166 .
- the Fischer-Tropsch derived base oils disclosed in EP-A-776959 , EP-A-668342 , WO-A-97/21788 , WO-00/15736 , WO-00/14188 , WO-00/14187 , WO-00/14183 , WO-00/14179 , WO-00
- Synthetic processes enable molecules to be built from simpler substances or to have their structures modified to give the precise properties required.
- Synthetic lubricant base oils include hydrocarbon oils such as olefin oligomers (also known as polyalphaolefins (PAOs)). Synthetic hydrocarbon base oils sold by the Shell Group under the designation "XHVI” (trade mark) may be conveniently used.
- hydrocarbon oils such as olefin oligomers (also known as polyalphaolefins (PAOs)).
- PAOs polyalphaolefins
- Lubricating oil base oils for use in the lubricating oil composition of the present invention are Group I, Group II or Group III base oils, polyalphaolefins, Fischer-Tropsch derived base oils and mixtures thereof.
- Group I base oil, Group II base oil and “Group III” base oil in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum Institute (API) categories I, II and III. Such API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002 .
- API American Petroleum Institute
- Group I base oils contain less than 90 % saturates (according to ASTM D2007) and/or greater than 0.03 % sulphur (according to ASTM D2622, D4294, D4927 or D3120) and have a viscosity index of greater than or equal to 80 and less than 120 (according to ASTM D2270).
- Group II base oils contain greater than or equal to 90 % saturates and less than or equal to 0.03 % sulphur and have a viscosity index of greater than or equal to 80 and less than 120, according to the aforementioned ASTM methods.
- Group III base oils contain greater than or equal to 90 % saturates and less than or equal to 0.03 % sulphur and have a viscosity index of greater than 120, according to the afore-mentioned ASTM methods.
- polyalphaolefins and their manufacture are well known in the art.
- Preferred polyalphaolefins that may be used in lubricating oil compositions of the present invention may be derived from C 2 to C 32 alpha olefins.
- feedstocks for said polyalphaolefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.
- lubricating oil base oils that may be conveniently used in the lubricating oil compositions of the present invention have a kinematic viscosity at 100 °C in the range of from 3 to 300 mm 2 /s, more preferably in the range of from 4 to 100 mm 2 /s.
- the lubricating oil composition of the present invention has a kinematic viscosity in the range of from 32 to 150 mm 2 /s at 40 °C, more preferably in the range of from 32 to 100 mm 2 /s, and most preferably in the range of from 32 to 68 mm 2 /s.
- Said additional base oil component is present in the lubricating oil composition of the present invention in an amount in the range of from 0.01 to 10.0 wt. %, more preferably above 1.0 wt. %, even more preferred above 2.0 wt. % based on the total weight of the lubricating oil composition.
- additional base oil components selected from bright stock oils, polyalkylene glycols (PAGs), alkyl naphthalenes, alkyl benzenes and natural and synthetic esters such as diesters and polyol esters may be used, the combined amount then preferably being in the range of from 0.01 to 10.0 wt. % based on the total weight of the lubricating oil composition.
- Bright stock oil is known in the art and is described, for example in GB-A-1496045 and US-A-4592832 .
- Bright stock oil is typically prepared by de-asphalting mineral-derived vacuum residue, for example, in the presence of propane.
- the resulting de-asphalted oil (DAO) then undergoes an upgrading process such as solvent extraction (or hydroprocessing), for example with furfural or NMP, in order to extract de-asphalted cylinder oil (DACO) therefrom.
- the resulting bright stock waxy raffinate is then de-waxed utilising, for example, methyl ethyl ketone (MEK) and/or toluene to remove bright stock slack wax therefrom.
- the resulting bright stock oil may then undergo optional hydrofinishing.
- the bright stock oil has a kinematic viscosity at 100 °C in the range of from 20 to 40 mm 2 /s, more preferably in the range of from 25 to 38 mm 2 /s, even more preferably in the range of from 30 to 34 mm 2 /s as determined according to ASTM D445.
- the lubricating oil composition of the present invention can further comprise one or more additives such as anti-oxidants, extreme pressure additives, other anti-wear additives than ashless thiophosphates, metal passivators such as copper passivators, corrosion inhibitors, foam inhibitors and/or demulsifiers.
- additives such as anti-oxidants, extreme pressure additives, other anti-wear additives than ashless thiophosphates, metal passivators such as copper passivators, corrosion inhibitors, foam inhibitors and/or demulsifiers.
- the lubricating oil composition of the present invention comprises one or more diphenylamine antioxidants.
- the one or more diphenylamines can be substituted or non-substituted. It is preferred to use a hydrocarbyl substituted diphenylamine, more preferably an alkyl substituted diphenylamine.
- Preferred diphenylamines are monoalkyldiphenylamines, dialkyldiphenylamines and bis(dialkylphenyl)amines.
- the alkyl group preferably contains between 2 and 15 carbon atoms, more preferably between 5 and 12 carbon atoms.
- diphenylamines include dialkyldiphenylamines such as p,p'-dioctyl-diphenylamine, p,p'-di- ⁇ -methylbenzyl-diphenylamine and N-p-butylphenyl-N-p'-octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine, bis(dialkylphenyl)amines such as di-(2,4-diethylphenyl)amine and di(2-ethyl-4-nonylphenyl)amine.
- dialkyldiphenylamines such as p,p'-dioctyl-diphenylamine, p,p'-di- ⁇ -methylbenzyl-diphenylamine and N-p-butylphenyl-N-p'-octylphenylamine
- the one or more diphenylamines are preferably present in the lubricating oil composition of the present invention in a total amount in the range of from 0.01 to 3.0 wt. %, more preferably in the range of from 0.01 to 1.0 wt. %, based on the total weight of the lubricating oil composition.
- Anti-wear additives that may be conveniently used include zinc dithiophosphate compounds selected from zinc dialkyl-, diaryl- and/or alkylaryl- dithiophosphates, molybdenum-containing compounds, boron-containing compounds and ashless anti-wear additives such as substituted or unsubstituted thiophosphoric acids, and salts thereof.
- Said anti-wear additives may each be conveniently added to the lubricating oil composition of the present invention in an amount in the range of from 0.1 to 3.0 wt. %, based on the total weight of lubricating oil composition.
- molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, for example as described in WO-A-98/26030 , sulphides of molybdenum and molybdenum dithiophosphate.
- Boron-containing compounds that may be conveniently used include borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.
- Demulsifiers which may be conveniently used in the lubricating oil composition of the present invention are polyalkylene glycol ethers or amines.
- the amount of said additives to be present in the lubricating composition depends on the specific compounds used.
- the lubricating oil composition of the present invention preferably comprises in the range of from 0.01 to 3.0 wt. %, more preferably in the range of from 0.01 to 1.0 wt. % of one or more substituted phenyl-naphthylamines (a), in the range of from 0.01 to 1.0 wt. %, more preferably in the range of from 0.01 to 0.1 wt. %, of one or more ashless thiophosphates (b), at least 85 wt. % by weight of lubricating oil base oil, preferably mineral oil base oil; and wherein said lubricating oil base oil comprises an amount in the range of from 0.01 to 10.0 wt.
- an additional base oil component being a bright stock oil with a kinematic viscosity at 100 °C in the range of from 20 to 40 mm 2 /s as determined according to ASTM D445, all based on total weight of the lubricating oil composition.
- the present invention further relates to the use of the lubricating oil composition according to the invention to lubricate a combination of a gas turbine and a steam turbine, more preferably such combination utilising a pressurised-steam generator.
- the present invention further provides the use of the lubricating oil composition of the present invention in order to reduce lacquer formation in a turbine as measured by a modified Wolf Strip test (formerly known as DIN 51392) with an oil volume of 150 ml, a pumping rate of 50 ml/hour, a plate temperature of 205 °C and a test duration of 24 hours, preferably in a combination of a gas turbine and a steam turbine and a method of reducing lacquer formation in a turbine, preferably in a combination of a gas turbine and a steam turbine, by lubricating said turbine(s) with a lubricating oil composition according to the present invention.
- a modified Wolf Strip test originally known as DIN 51392
- DIN 51392 modified Wolf Strip test
- the lubricating composition may be conveniently prepared by blending together one or more substituted phenyl-naphthylamines (a), one or more ashless thiophosphates (b), the lubricating oil base oil and, an additional base oil component being a bright stock oil as hereinbefore described and/or one or more additives.
- Tables 1 and 2 are in wt. %, based on the total weight of the formulations.
- the substituted phenyl-naphthylamine (a) used in the formulations of Tables 1 and 2 was that available from Ciba Specialty Chemicals under the trade designation "IRGANOX L-06".
- the ashless thiophosphates (b) used in the formulations of Tables 1 and 2 are designated herein as "Ashless thiophosphate (b)-1” and “Ashless thiophosphate (b)-2".
- "Ashless thiophosphate (b)-1” and “Ashless thiophosphate (b)-2” are available from Ciba Specialty Chemicals under the trade designation "IRGALUBE 353" and from Lubrizol under the trade designation "LZ 5125", respectively.
- the diphenylamine antioxidant used in the formulations of Tables 1 and 2 was that available from Ciba Specialty Chemicals under the trade designation "IRGANOX L-57”.
- Tables 1 and 2 also comprised an additive combination of conventional additives in conventional amounts to act as rust inhibitors, copper passivators, demulsifiers and foam inhibitors.
- the lubricating oil base oil used in the formulations of Tables 1 and 2 was a Group II mineral oil and the additional base oil component was bright stock oil.
- Example 4 is according to the present invention whilst the remaining Example in Table 2 is comparative in nature.
- DIN 51392 formerly measured the tendency of engine oils to produce thermal/oxidative deposits using an inclined metal plate over which the test engine oils were pumped.
- the volume of oil, pumping rate, plate temperature and test duration specified in said test were 200 ml, 50 ml/hour, 250 °C and 12 hours, respectively.
- test conditions used in the Examples of Tables 1 and 2 were modified to an oil volume of 150 ml, a pumping rate of 50 ml/hour, a plate temperature of 205 °C and a test duration of 24 hours.
- Table 2 The formulations in Table 2 were also subjected to the Oxidation Stability of Steam Turbine Oils test (TOST)(1000 hours, ASTM D4310-03) to measure sludge and the Cincinnati Machine Test Procedure A (ASTM D 2070-91) to measure sludge.
- TOST Oxidation Stability of Steam Turbine Oils test
- ASTM D4310-03 ASTM D4310-03
- ASTM D 2070-91 Cincinnati Machine Test Procedure A
- the methodology used for the TOST 1000 hours (ASTM D 4310-03) was to heat 300 ml of the test lubricating oil composition with 60 ml of water to 95 °C, in the presence of a copper and a steel coil catalyst, blowing the test mixture with oxygen for 1000 hours. After 1000 hours, the weight of insoluble material was determined by filtering the lubricating oil composition through a 5 micron filter.
- test lubricating oil composition was heated 200 ml of the test lubricating oil composition in a beaker, in the presence of a copper and a steel rod, to 135 °C in an oven for 168 hours. After 168 hours, the appearance of the copper and steel rods was visually rated and the weight of insoluble material was determined by filtering the lubricating oil composition through 20 and 8 micron filters.
- Example 4 shows greatly reduced deposit formation tendency compared to the formulation of Comparative Example 1.
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Description
- The present invention relates to lubricating oil compositions, more specifically to lubricating oil compositions for lubricating turbines and in particular, to lubricating oil compositions for lubricating a combination of a steam turbine and a gas turbine.
- The use of a combination of a gas turbine and a steam turbine for power generation, has the advantage that it is more efficient than power generation with either type of turbine. The combination will hereinafter also be referred to as "combined cycle".
- A difficulty of lubricating a combined cycle resides in the large variety of different components which must be lubricated, i.e. bearings (both journal and thrust), gears, hydraulic control systems, flexible couplings and oil shaft seals. Although each component could be lubricated per se, it is advantageous to have a single, common lubricating system containing a single, common lubricant for all components.
- The lubricating oil composition for use in the common system has to meet a rather outstanding combination of requirements in order to satisfactorily lubricate each component. These requirements comprise the rather severe thermal and oxidative stability requirements and stringent foaming levels for the gas turbine part, whereas the steam turbine part requires the oil to have good water shedding properties and excellent corrosion resistance.
- High temperature oxidative stability means that the lubricating oil composition has a low tendency to form sludge, a low increase in viscosity and a low increase in total acid number at high temperature. Desirable characteristics are a viscosity increase of at most 20 %, a total acid number increase of at most 3.0 mg KOH/g and a sludge content of less than 300 mg/100 ml after having been subjected to the oxidation stability test DIN 51394 performed according to the high temperature modifications set out in the General Electric specifications GEK 32568 C and GEK 101941, preferably less than 250 ml/g, more preferably less than 200 ml/g, most preferably less than 150 ml/g. In establishing the amount of sludge produced, the sludge must be removed carefully from all the equipment used in the test. The sludge is separated from the oil by filtration.
- The tendency of a lubricating oil composition to form sludge is an important factor in whether it will be suitable for use in lubricating combined cycle equipment.
- A lubricating oil composition for use in combined cycle equipment must further have a certain viscosity index, pour point, filterability and anti-wear performance, while the composition should provide adequate lubrication over many years.
- Achieving this combination of complex lubricant properties allows the lubricating oil composition to be suitable for use in combined cycle equipment.
- However, in addition to sludge formation, the degradation of lubricating oil compositions such as turbine oils in service can also result in lacquers and other deposits. Such lacquers and deposits also shorten the life of lubricating oil compositions such as turbine oils, thereby reducing the service interval of a turbine or resulting in expensive and unplanned turbine shutdowns.
- Depending on turbine type and operating conditions, the typical lifetime of a turbine oil can be approximately 5 to 10 years or more. Thus, in addition to sludge reduction, it is important that the formation of lacquers and other deposits are also reduced.
- Although industrial standard oil performance tests are able to indicate the probability of a lubricating oil composition forming oxidative sludges, these tests are not able to predict accurately the likelihood of a lubricating oil composition forming lacquers in service.
- Herein a predictive lacquer formation test for lubricating oil compositions such as turbine oils is disclosed which is a modified version of the Wolf Strip test as per ex. DIN 51392.
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EP-A-0696636 describes a lubricating oil composition for use in internal combustion engines which comprises a combination of (A) a lubricating base oil, (B) one or more alkyl diphenylamines and/or one or more phenyl-α-naphthylamines and (C) oxymolybdenum sulfide dithiocarbamate and/or oxymolybdenum sulfide organophosphorodithioate. - In the examples of
EP-A-0696636 , either a single alkyl diphenylamine or a single phenyl-α-naphthylamine is used. Oxymolybdenum sulfide organophosphorodithioate is present in only one of the examples according to the teaching. However,EP-A-0696636 is not concerned with reducing lacquer formation in turbines and does not disclose or teach any lubricating oil compositions for this purpose. -
GB-B-0990097 - However, said document is not directed to the problem of reducing lacquer formation in combined cycle equipment and it does not disclose or teach the specific lubricating oil composition of the present invention.
-
DE-A-1594405 describes lubricating oil compositions for steam turbines comprising mineral oil and (a) an aliphatic polycarboxylic acid containing at least 12 carbon atoms, (b) an alkylphenol, (c) an aromatic amine, and (d) a dialkyldithiophosphate. -
DE-A-1594405 states that aromatic amines normally have a tendency to form sludge and have unsatisfactory light stability, whilst the lubricating oil compositions in accordance withDE-A-1594405 have better stability. - The aromatic amine (c) in
DE-A-1594405 may be a secondary aromatic amine such as diphenylamine, phenyl-alpha- or -beta-naphthylamine and alkyl substituted analogues such as p,p'-dioctyldiphenylamine. -
US 3 923 672 discloses a lubricating composition particularly suitable for use in steam turbines or gas turbines. -
FR 2 832 417 -
US 3 844 963 discloses a lubricating composition comprising a base oil and a dithiophosphoric acid derivative. No bright stock oil is mentioned. -
US 2003/096713 discloses a lubricating composition comprising a base oil, one or more antioxidants and from 0.01 wt.% to 3 wt.% of at least one dispersant or detergent, wherein the total amount of antioxidant is at least 2 wt.%. No bright stock oil is mentioned. -
US 5 726 135 discloses a lubricating composition for aircraft and turbo engine end-use application comprising a synthetic base oil and an alkylated or alkarylated dithiocarbamate, wherein the composition is absolutely free of phosphorus, metals, metal salts, and detergent/diapersant. No bright stock oil is mentioned. -
US 5 520 830 discloses a method of reducing the level of oxidation of a lubricant, which comprises incorporating soluble copper in the lubricant in an amount above 1200 ppm. No bright stock oil is mentioned. -
WO 98/02510 -
WO-A-99/43770 - In the examples of
WO-A-99/43770 -
WO-A-99/43770 WO-A-99/43770 - There has now been surprisingly found a lubricating oil composition comprising a specific combination of components, which composition not only meets the requirements for use in a combined cycle as disclosed in
WO-A-99/43770 - Accordingly, the present invention provides a lubricating oil composition according to claim 1.
- The one or more substituted phenyl-naphthylamines (a) which are used in the present invention, can be used as such or in the form of a salt. Examples of such substituted phenyl-naphthylamines are substituted phenyl-alpha-naphthylamines and substituted phenyl-beta-naphthylamines. The one or more substituted phenyl-naphthylamines are preferably substituted phenyl-alpha-naphthylamines.
- Preferred substituted phenyl-naphthylamines are alkylated phenyl-alpha-naphthylamines and/or alkylated phenyl-beta-naphthylamines. More preferably, said substituted phenyl-naphthylamines are mono-alkylated phenyl-alpha-naphthylamines and/or mono-alkylated phenyl-beta-naphthylamines.
- Particularly preferred mono-alkylated phenyl-alpha-naphthylamines and mono-alkylated phenyl-beta-naphthylamines are those wherein the alkyl substituents are straight chain or branched alkyl groups having in the range of from 1 to 18 carbon atoms.
- Examples of substituted phenyl-naphthylamines that may be conveniently used include octylphenyl-beta-naphthylamine, t-octylphenyl-alpha-naphthylamine, p-octylphenyl-alpha-naphthylamine, 4-octylphenyl-1-octyl-beta-naphthylamine, n-t-dodecylphenyl-1-naphthylamine, N-hexylphenyl-2-naphthylamine. A particularly preferred substituted phenyl-alpha-naphthylamine is a monooctylated phenyl alpha-naphthylamine.
- Substituted phenyl-naphthylamines as commercially available can be used in the present invention. An example of a commercially available substituted phenyl-naphthylamine that may be conveniently used in the lubricating oil composition of the present invention is that available from Ciba Specialty Chemicals under the trade designation "IRGANOX L=06".
- As anti-wear additives one or more thiophosphates are used, preferably one or more ashless thiophosphates. Ashless thiophosphates are known in the art. These compounds are metal-free organic compounds.
- The one or more ashless thiophosphates may be esters and/or salts of thiophosphoric acids, substituted thiophosphoric acids. Preferably, the ashless thiophosphates are substituted by one or more hydrocarbyl groups which hydrocarbyl groups can optionally contain an acid, a hydroxy and/or an ester group. The hydrocarbyl moiety preferably is an alkyl containing up to 12 carbon atoms. The hydrocarbyl substituted thiophosphate preferably contains 2 or 3 hydrocarbyl groups, or is a mixture of thiophosphates containing 2 and 3 hydrocarbyl groups.
- The ashless thiophosphates can contain any number of sulphur atoms directly linked to the phosphorus atom. Preferably, the thiophosphates are monothiophosphates and/or dithiophosphates.
- Examples of ashless thiophosphates which may be conveniently used in the lubricating oil composition of the present invention are described in
EP-A-0375324 ,US-A-5922657 ,US-A-4333841 andUS-A-5093016 and may be conveniently made according to the methods described therein. - The one or more ashless thiophosphates are preferably compounds according to formula (I)
- Preferably, R1 and R2 are each, independently, selected from hydrogen, branched or straight chain C3 to C18 alkyl groups, C5 to C12 cycloalkyl groups, C5 to C9 cycloalkylmethyl groups, C9 to C10 bicycloalkylmethyl groups, C9 to C10 tricycloalkylmethyl groups, phenyl or C7 to C24 alkylphenyl groups or R1 and R2 together may be a C2 to C12 alkylene group which may be interrupted by 1 or 2 oxygen atoms.
- More preferably, R1 and R2 are each, independently, selected from hydrogen, branched or straight chain C3 to C18 alkyl groups selected from propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethylhexyl and 1-methylundecyl, phenyl and C7 to C24 alkylphenyl groups selected from methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, isopropylphenyl, t-butylphenyl, di-t-butylphenyl and 2,6-di-t-butyl-4-methylphenyl.
- With regard to the CR3R4 repeating unit in the compound of formula (I), R3 and R4 groups in each repeating unit may be the same or different from R3 and R4 groups in other repeating units.
- In a preferred embodiment, R3 and R4 are each selected, independently, from hydrogen, methyl and ethyl.
- In a more preferred embodiment of the present invention, the one or more ashless thiophosphates are preferably compounds according to formula (II)
- Preferably, R8 and R9 are each, independently, selected from hydrogen, branched or straight chain C3 to C18 alkyl groups, C5 to C12 cycloalkyl groups, C5 to C9 cycloalkylmethyl groups, C9 to C10 bicycloalkylmethyl groups, C9 to C10 tricycloalkylmethyl groups, phenyl or C7 to C24 alkylphenyl groups or R8 and R9 together may be a C2 to C12 alkylene group which may be interrupted by 1 or 2 oxygen atoms.
- More preferably, R8 and R9 are each, independently, selected from hydrogen, branched or straight chain C3 to C18 alkyl groups selected from propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1,3-trimethylhexyl and 1-methylundecyl, phenyl and C7 to C24 alkylphenyl groups selected from methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, isopropylphenyl, t-butylphenyl, di-t-butylphenyl and 2,6-di-t-butyl-4-methylphenyl.
- In a preferred embodiment, R10 is selected from hydrogen, methyl and ethyl.
- Examples of commercially available ashless thiophosphates that may be conveniently used in the lubricating oil composition of the present invention include those available from Ciba Specialty Chemicals under the trade designations "IRGALUBE L-63" and "IRGALUBE 353" and that available from Lubrizol under the trade designation "LZ 5125".
- The amount of the additives (a) and (b) present in the lubricating oil composition of the present invention, depends on the specific compounds used therein.
- The one or more substituted phenyl-naphthylamines (a) are present in the lubricating oil composition of the present invention in a total amount in the range of from 0.01 to 3.0 wt. %, preferably in the range of from 0.01 to 1.0 wt. %, based on the total weight of the lubricating oil composition.
- The one or more ashless thiophosphates are preferably present in the lubricating oil composition of the present invention in a total amount in the range of from 0.01 to 1.0 wt. %, more preferably in the range of from 0.01 to 0.1 wt. %, based on the total weight of the lubricating oil composition.
- The lubricating oil base oil in the lubricating oil composition of the present invention may be selected from mineral and/or synthetic lubricant base oils.
- Said lubricating oil base oil is preferably present in an amount of at least 85 wt. %, more preferably at least 90 wt. %, based on the total weight of the lubricating oil composition.
- Mineral lubricant base oils that may be conveniently used include liquid petroleum oils and solvent treated or acid treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrocracking and hydrofinishing processes and/or dewaxing.
- Naphthenic base oils have low viscosity index (VI) (generally 40-80) and a low pour point. Such base oils are produced from feedstocks rich in naphthenes and low in wax content and are used mainly for lubricants in which colour and colour stability are important, and VI and oxidation stability are of secondary importance.
- Paraffinic base oils have higher VI (generally >95) and a high pour point. Said base oils are produced from feedstocks rich in paraffins, and are used for lubricants in which VI and oxidation stability are important.
- Fischer-Tropsch derived base oils may be conveniently used as the lubricating oil base oil in the lubricating oil composition of the present invention, for example, the Fischer-Tropsch derived base oils disclosed in
EP-A-776959 EP-A-668342 WO-A-97/21788 WO-00/15736 WO-00/14188 WO-00/14187 WO-00/14183 WO-00/14179 WO-00/08115 WO-99/41332 EP-1029029 ,WO-01/18156 WO-01/57166 - Synthetic processes enable molecules to be built from simpler substances or to have their structures modified to give the precise properties required.
- Synthetic lubricant base oils include hydrocarbon oils such as olefin oligomers (also known as polyalphaolefins (PAOs)). Synthetic hydrocarbon base oils sold by the Shell Group under the designation "XHVI" (trade mark) may be conveniently used.
- Lubricating oil base oils for use in the lubricating oil composition of the present invention are Group I, Group II or Group III base oils, polyalphaolefins, Fischer-Tropsch derived base oils and mixtures thereof.
- By "Group I" base oil, "Group II" base oil and "Group III" base oil in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum Institute (API) categories I, II and III. Such API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
- Group I base oils contain less than 90 % saturates (according to ASTM D2007) and/or greater than 0.03 % sulphur (according to ASTM D2622, D4294, D4927 or D3120) and have a viscosity index of greater than or equal to 80 and less than 120 (according to ASTM D2270).
- Group II base oils contain greater than or equal to 90 % saturates and less than or equal to 0.03 % sulphur and have a viscosity index of greater than or equal to 80 and less than 120, according to the aforementioned ASTM methods.
- Group III base oils contain greater than or equal to 90 % saturates and less than or equal to 0.03 % sulphur and have a viscosity index of greater than 120, according to the afore-mentioned ASTM methods.
- As described in
US-B1-6180575 andUS-A-5602086 , polyalphaolefins and their manufacture are well known in the art. Preferred polyalphaolefins that may be used in lubricating oil compositions of the present invention may be derived from C2 to C32 alpha olefins. - Particularly preferred feedstocks for said polyalphaolefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.
- Preferably, lubricating oil base oils that may be conveniently used in the lubricating oil compositions of the present invention have a kinematic viscosity at 100 °C in the range of from 3 to 300 mm2/s, more preferably in the range of from 4 to 100 mm2/s.
- Preferably, the lubricating oil composition of the present invention has a kinematic viscosity in the range of from 32 to 150 mm2/s at 40 °C, more preferably in the range of from 32 to 100 mm2/s, and most preferably in the range of from 32 to 68 mm2/s.
- Said additional base oil component is present in the lubricating oil composition of the present invention in an amount in the range of from 0.01 to 10.0 wt. %, more preferably above 1.0 wt. %, even more preferred above 2.0 wt. % based on the total weight of the lubricating oil composition. It goes without saying that also two or more additional base oil components selected from bright stock oils, polyalkylene glycols (PAGs), alkyl naphthalenes, alkyl benzenes and natural and synthetic esters such as diesters and polyol esters may be used, the combined amount then preferably being in the range of from 0.01 to 10.0 wt. % based on the total weight of the lubricating oil composition.
- As an additional base oil component bright stock oil is used.
- Bright stock oil is known in the art and is described, for example in
GB-A-1496045 US-A-4592832 . Bright stock oil is typically prepared by de-asphalting mineral-derived vacuum residue, for example, in the presence of propane. The resulting de-asphalted oil (DAO) then undergoes an upgrading process such as solvent extraction (or hydroprocessing), for example with furfural or NMP, in order to extract de-asphalted cylinder oil (DACO) therefrom. The resulting bright stock waxy raffinate is then de-waxed utilising, for example, methyl ethyl ketone (MEK) and/or toluene to remove bright stock slack wax therefrom. The resulting bright stock oil may then undergo optional hydrofinishing. - The bright stock oil has a kinematic viscosity at 100 °C in the range of from 20 to 40 mm2/s, more preferably in the range of from 25 to 38 mm2/s, even more preferably in the range of from 30 to 34 mm2/s as determined according to ASTM D445.
- The lubricating oil composition of the present invention can further comprise one or more additives such as anti-oxidants, extreme pressure additives, other anti-wear additives than ashless thiophosphates, metal passivators such as copper passivators, corrosion inhibitors, foam inhibitors and/or demulsifiers.
- In a preferred embodiment, the lubricating oil composition of the present invention comprises one or more diphenylamine antioxidants.
- The one or more diphenylamines can be substituted or non-substituted. It is preferred to use a hydrocarbyl substituted diphenylamine, more preferably an alkyl substituted diphenylamine. Preferred diphenylamines are monoalkyldiphenylamines, dialkyldiphenylamines and bis(dialkylphenyl)amines. The alkyl group preferably contains between 2 and 15 carbon atoms, more preferably between 5 and 12 carbon atoms.
- Particularly preferred diphenylamines include dialkyldiphenylamines such as p,p'-dioctyl-diphenylamine, p,p'-di-α-methylbenzyl-diphenylamine and N-p-butylphenyl-N-p'-octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine, bis(dialkylphenyl)amines such as di-(2,4-diethylphenyl)amine and di(2-ethyl-4-nonylphenyl)amine.
- Examples of commercially available diphenylamines that may be conveniently used in the lubricating oil composition of the present invention include that available from Ciba Specialty Chemicals under the trade - designation "IRGANOX L-57".
- The one or more diphenylamines are preferably present in the lubricating oil composition of the present invention in a total amount in the range of from 0.01 to 3.0 wt. %, more preferably in the range of from 0.01 to 1.0 wt. %, based on the total weight of the lubricating oil composition.
- Anti-wear additives that may be conveniently used include zinc dithiophosphate compounds selected from zinc dialkyl-, diaryl- and/or alkylaryl- dithiophosphates, molybdenum-containing compounds, boron-containing compounds and ashless anti-wear additives such as substituted or unsubstituted thiophosphoric acids, and salts thereof..
- Said anti-wear additives may each be conveniently added to the lubricating oil composition of the present invention in an amount in the range of from 0.1 to 3.0 wt. %, based on the total weight of lubricating oil composition.
- Examples of such molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, for example as described in
WO-A-98/26030 - Boron-containing compounds that may be conveniently used include borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.
- Compounds such as alkenyl succinic acid or ester moieties thereof, benzotriazole-based compounds and thiodiazole-based compounds may be conveniently used in the lubricating oil composition of the present invention as corrosion inhibitors.
- Compounds such as polysiloxanes, dimethyl polycyclohexane and polyacrylates may be conveniently used in the lubricating oil composition of the present invention as foam inhibitors.
- Demulsifiers which may be conveniently used in the lubricating oil composition of the present invention are polyalkylene glycol ethers or amines.
- The amount of said additives to be present in the lubricating composition, depends on the specific compounds used.
- The lubricating oil composition of the present invention preferably comprises in the range of from 0.01 to 3.0 wt. %, more preferably in the range of from 0.01 to 1.0 wt. % of one or more substituted phenyl-naphthylamines (a), in the range of from 0.01 to 1.0 wt. %, more preferably in the range of from 0.01 to 0.1 wt. %, of one or more ashless thiophosphates (b), at least 85 wt. % by weight of lubricating oil base oil, preferably mineral oil base oil; and wherein said lubricating oil base oil comprises an amount in the range of from 0.01 to 10.0 wt. % of an additional base oil component being a bright stock oil with a kinematic viscosity at 100 °C in the range of from 20 to 40 mm2/s as determined according to ASTM D445, all based on total weight of the lubricating oil composition.
- The present invention further relates to the use of the lubricating oil composition according to the invention to lubricate a combination of a gas turbine and a steam turbine, more preferably such combination utilising a pressurised-steam generator.
- Also described is a method of lubricating a combination of a gas turbine and a steam turbine utilising a pressurised-steam generator by employing the lubricating oil composition of the present invention.
- In addition, the present invention further provides the use of the lubricating oil composition of the present invention in order to reduce lacquer formation in a turbine as measured by a modified Wolf Strip test (formerly known as DIN 51392) with an oil volume of 150 ml, a pumping rate of 50 ml/hour, a plate temperature of 205 °C and a test duration of 24 hours, preferably in a combination of a gas turbine and a steam turbine and a method of reducing lacquer formation in a turbine, preferably in a combination of a gas turbine and a steam turbine, by lubricating said turbine(s) with a lubricating oil composition according to the present invention.
- The lubricating composition may be conveniently prepared by blending together one or more substituted phenyl-naphthylamines (a), one or more ashless thiophosphates (b), the lubricating oil base oil and, an additional base oil component being a bright stock oil as hereinbefore described and/or one or more additives.
- The present invention is described below with reference to the following Examples, which are not intended to limit the scope of the invention in any way.
- Formulations were blended using the base oils and additives specified in Tables 1 and 2.
- The amounts in Tables 1 and 2 are in wt. %, based on the total weight of the formulations.
- The substituted phenyl-naphthylamine (a) used in the formulations of Tables 1 and 2 was that available from Ciba Specialty Chemicals under the trade designation "IRGANOX L-06".
- The ashless thiophosphates (b) used in the formulations of Tables 1 and 2 are designated herein as "Ashless thiophosphate (b)-1" and "Ashless thiophosphate (b)-2". "Ashless thiophosphate (b)-1" and "Ashless thiophosphate (b)-2" are available from Ciba Specialty Chemicals under the trade designation "IRGALUBE 353" and from Lubrizol under the trade designation "LZ 5125", respectively.
- The diphenylamine antioxidant used in the formulations of Tables 1 and 2 was that available from Ciba Specialty Chemicals under the trade designation "IRGANOX L-57".
- The formulations of Tables 1 and 2 also comprised an additive combination of conventional additives in conventional amounts to act as rust inhibitors, copper passivators, demulsifiers and foam inhibitors.
- The lubricating oil base oil used in the formulations of Tables 1 and 2 was a Group II mineral oil and the additional base oil component was bright stock oil.
- Examples 1 to 3 are according to the present invention whilst the remaining Examples in Table 1 are comparative in nature.
- In Table 2, Example 4 is according to the present invention whilst the remaining Example in Table 2 is comparative in nature.
- The formulations in Tables 1 and 2 were tested for lacquer formation in a version of the Wolf Strip Test (formerly known as DIN 51392) performed according to the modifications set out below.
- DIN 51392 formerly measured the tendency of engine oils to produce thermal/oxidative deposits using an inclined metal plate over which the test engine oils were pumped. The volume of oil, pumping rate, plate temperature and test duration specified in said test were 200 ml, 50 ml/hour, 250 °C and 12 hours, respectively.
- In order to improve the test repeatability and to more closely simulate the type of thermal/oxidative stress that a lubricating oil composition would experience under full hydrodynamic film conditions in a turbine, the test conditions used in the Examples of Tables 1 and 2 were modified to an oil volume of 150 ml, a pumping rate of 50 ml/hour, a plate temperature of 205 °C and a test duration of 24 hours.
- The formulations in Table 2 were also subjected to the Oxidation Stability of Steam Turbine Oils test (TOST)(1000 hours, ASTM D4310-03) to measure sludge and the Cincinnati Machine Test Procedure A (ASTM D 2070-91) to measure sludge.
- The methodology used for the TOST (1000 hours) (ASTM D 4310-03) was to heat 300 ml of the test lubricating oil composition with 60 ml of water to 95 °C, in the presence of a copper and a steel coil catalyst, blowing the test mixture with oxygen for 1000 hours. After 1000 hours, the weight of insoluble material was determined by filtering the lubricating oil composition through a 5 micron filter.
- The methodology used for the Cincinnati Machine Test Procedure A (ASTM D 2070-91) was to heat 200 ml of the test lubricating oil composition in a beaker, in the presence of a copper and a steel rod, to 135 °C in an oven for 168 hours. After 168 hours, the appearance of the copper and steel rods was visually rated and the weight of insoluble material was determined by filtering the lubricating oil composition through 20 and 8 micron filters.
- It is apparent from Tables 1 and 2 that the formulations in accordance with the present invention not only exhibit good sludge deposit control, but also display outstanding performance in reducing lacquer formation as measured in the modified Wolf Strip test outlined above.
- After repeating the Experiments of Examples 1 to 3, whilst replacing the Group II mineral base oil.by a Fischer-Tropsch derived Group III base oil, it was shown that the addition of bright stock oil resulted in reduced lacquer formation as measured in the modified Wolf Strip test outlined above.
TABLE 1 Ex. 1 Ex. 2 Ex. 3 Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3 Comp. Ex. 4 Substituted phenyl-α-naphthylamine (a) (% wt.) 0.5 0.5 0.5 - * ** *** Non-substituted phenyl-α-naphthylamine (% wt.) - - - 0.5 Ashless thiophosphate (b)-1 (% wt.) 0.05 0.05 0.05 - Ashless thiophosphate (b)-2(% wt.) - - - 0.1 Diphenylamine (% wt.) 0.5 0.5 0.5 0.5 Other additives (% wt.) 0.1075 0.1075 0.1075 0.1575 Bright stock oil (% wt.) - 2.5 5.0 - Group II mineral base oil Balance Balance Balance Balance Wolf Strip Test (modified DIN 51392) (205 °C, 24 hours) (mg) 39.6 15.4 14.2 97.6 66.8 137.0 61.6 nm = not measured.
* Commercial turbine oil 1.
** Commercial turbine oil 2.
*** Commercial turbine oil 3.TABLE 2 Ex. 4 Comp. Ex. 1 Substituted phenyl-α-naphthylamine (a) (% wt.) 0.7 - Non-substituted phenyl-α-naphthylamine (% wt.) - 0.5 Ashless thiophosphate (b)-1 (% wt.) 0.05 - Ashless thiophosphate (b)-2 (% wt.) - 0.1 Diphenylamine (% wt.) 0.7 0.5 Other additives (% wt.) 0.1075 0.1575 Bright stock oil (% wt.) 2.5 - Group II mineral base oil Balance Balance Wolf Strip Test (modified DIN 51392) (205 °C, 24 hours) (mg) <10 97.6 TOST 1,000 hrs sludge test, ASTM D4310-03 (mg) 33 57 Cincinnati Machine Test Procedure A (ASTM D 2070-91), sludge (mg per 100 ml) 10.7 64.2 - It is apparent from the results of Table 2 that the formulation of Example 4 shows greatly reduced deposit formation tendency compared to the formulation of Comparative Example 1.
Claims (11)
- Lubricating oil composition comprising lubricating oil base oil, the lubricating oil base oil being selected from the group consisting of Group 1, Group II or Group III base oils, polyalphaolefins, Fischer-Tropsch derived base oils and mixtures thereof, in combination with:(a) one or more substituted phenyl-naphthylamines being present in a total amount in the range of from 0.01 to 3.0 wt. %, based on the total weight of the lubricating oil composition;(b) one or more thiophosphates; and(c) an additional base oil component being present in an amount in the range of from 0.01 to 10.0 wt.%, based on the total weight of the lubricating oil composition, the additional base oil component being bright stock oil with a kinematic viscosity at 100 °C in the range of from 20 to 40 mm2/s as determined according to ASTM D445.
- Lubricating oil composition according to Claim 1, wherein said one or more substituted phenyl-naphthylamines (a) are selected from alkylated phenyl-alpha-naphthylamines and/or alkylated phenyl-beta-naphthylamines.
- Lubricating composition according to Claim 1 or 2, wherein said one or more thiophosphates are ashless thiophosphates.
- Lubricating composition according to Claim 3, wherein said one or more ashless thiophosphates (b) are compounds according to formula (I)
- Lubricating oil composition according to any one of Claims 3 to 4, wherein said one or more ashless thiophosphates (b) are present in a total amount in the range of from 0.01 to 1.0 wt.%, based on the total weight of the lubricating oil composition.
- Lubricating oil composition according to any one of Claims 1 to 5, wherein said lubricating oil composition further comprises one or more additives selected from anti-oxidants, extreme pressure additives, metal passivators, corrosion inhibitors, foam inhibitors and/or demulsifiers.
- Use of a lubricating oil composition according to any one of Claims 1 to 6 to lubricate a combination of a gas turbine and a steam turbine.
- Use of a lubricating oil composition according to any one of Claims 1 to 6 in order to reduce lacquer formation in a turbine, as measured by a modified Wolf Strip test (formerly known as DIN 51392) with an oil volume of 150 ml, a pumping rate of 50 ml/hour, a plate temperature of 205 °C and a test duration of 24 hours.
- Use of a lubricating oil composition according to Claim 8, wherein said turbine is in a combination of a gas turbine and a steam turbine.
- Method of reducing lacquer formation in a turbine by lubricating said turbine(s) with a lubricating oil composition according to any one of Claims 1 to 6.
- Method of reducing lacquer formation in a turbine according to Claim 10, wherein said turbine is in a combination of a gas turbine and a steam turbine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07728774.6A EP2021440B1 (en) | 2006-05-15 | 2007-05-03 | Lubricating oil composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06252528 | 2006-05-15 | ||
| PCT/EP2007/054321 WO2007131891A1 (en) | 2006-05-15 | 2007-05-03 | Lubricating oil composition |
| EP07728774.6A EP2021440B1 (en) | 2006-05-15 | 2007-05-03 | Lubricating oil composition |
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| Publication Number | Publication Date |
|---|---|
| EP2021440A1 EP2021440A1 (en) | 2009-02-11 |
| EP2021440B1 true EP2021440B1 (en) | 2015-07-01 |
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| EP07728774.6A Active EP2021440B1 (en) | 2006-05-15 | 2007-05-03 | Lubricating oil composition |
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| US (1) | US20090186789A1 (en) |
| EP (1) | EP2021440B1 (en) |
| JP (1) | JP5527758B2 (en) |
| CN (1) | CN101466818B (en) |
| WO (1) | WO2007131891A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8227391B2 (en) † | 2008-10-17 | 2012-07-24 | Afton Chemical Corporation | Lubricating composition with good oxidative stability and reduced deposit formation |
| WO2012080441A1 (en) * | 2010-12-17 | 2012-06-21 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| CN102925256B (en) * | 2011-08-10 | 2014-07-02 | 中国石油化工股份有限公司 | Heat-conductive oil composition having high temperature oxidation resistance |
| US10023824B2 (en) * | 2013-04-11 | 2018-07-17 | Afton Chemical Corporation | Lubricant composition |
| KR101831489B1 (en) * | 2014-08-27 | 2018-02-22 | 에스케이이노베이션 주식회사 | Lubricant Composition for Excellent Thermo-Oxidation Stability and Color Stability |
| JP6669343B2 (en) * | 2015-02-27 | 2020-03-18 | 出光興産株式会社 | Biodegradable lubricating oil composition |
| SG11201810528RA (en) * | 2016-06-28 | 2019-01-30 | Shell Int Research | Lubricating composition |
| CN109054946A (en) * | 2018-07-30 | 2018-12-21 | 郑州市欧普士科技有限公司 | A kind of environment-friendly type tractor Multipurpose oil and preparation method thereof |
| CN115505441A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Light-stable turbine oil composition, preparation method and application thereof |
| US20240336865A1 (en) * | 2021-08-03 | 2024-10-10 | Lanxess Deutschland Gmbh | Novel additive mixture |
| CN113773896B (en) * | 2021-09-18 | 2022-12-09 | 新乡市瑞丰新材料股份有限公司 | Extreme pressure type steam turbine oil complexing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1043280A (en) * | 1963-10-25 | 1966-09-21 | Shell Int Research | Improvements in or relating to lubricating oil compositions |
| BE785885A (en) * | 1971-07-06 | 1973-01-05 | Edwin Cooper & Cy Ltd | LUBRICANT IMPROVEMENTS |
| US3926823A (en) * | 1974-10-07 | 1975-12-16 | Continental Oil Co | Turbine oil compositions |
| US3923672A (en) * | 1974-10-07 | 1975-12-02 | Continental Oil Co | Turbine oil compositions |
| GB2056482A (en) * | 1979-08-13 | 1981-03-18 | Exxon Research Engineering Co | Lubricating oil compositions |
| US4592832A (en) * | 1984-09-06 | 1986-06-03 | Exxon Research And Engineering Co. | Process for increasing Bright Stock raffinate oil production |
| DK0496486T3 (en) * | 1991-01-11 | 1994-03-28 | Mobil Oil Corp | Lubricant Compositions |
| US5520830A (en) * | 1991-10-11 | 1996-05-28 | Akzo Nobel N.V. | Composition and process for retarding lubricant oxidation using copper additive |
| JP3422544B2 (en) * | 1993-11-30 | 2003-06-30 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| US20030096713A1 (en) * | 1994-04-19 | 2003-05-22 | Eric R. Schnur | Lubricating compositions with improved oxidation resistance containing a dispersant and an antioxidant |
| TR199900054T2 (en) * | 1996-07-12 | 1999-03-22 | Castrol Limited | Lubricant containing alkyl substituted naphthalene and ester. |
| US5726135A (en) * | 1996-12-11 | 1998-03-10 | Khorramian; Behrooz A. | Phosphorus-free and ashless oil for aircraft and turbo engine application |
| JP2002528559A (en) * | 1998-02-27 | 2002-09-03 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Lubricating composition |
| US6180575B1 (en) * | 1998-08-04 | 2001-01-30 | Mobil Oil Corporation | High performance lubricating oils |
| DE60226196T2 (en) * | 2001-05-24 | 2009-05-14 | Shipley Co., L.L.C., Marlborough | Tin-plating |
| CA2403540A1 (en) * | 2001-11-20 | 2003-05-20 | Bp Corporation North America Inc. | Synergystic combination of aryl amine antioxidants in aviation turbine oils |
| JP4524101B2 (en) * | 2003-12-25 | 2010-08-11 | 新日本石油株式会社 | Gas turbine apparatus and gas turbine apparatus lubrication method |
| JP4772284B2 (en) * | 2004-01-08 | 2011-09-14 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| JP4573541B2 (en) * | 2004-02-26 | 2010-11-04 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| JP2006016453A (en) * | 2004-06-30 | 2006-01-19 | Nippon Oil Corp | Lubricating oil composition for internal combustion engine |
-
2007
- 2007-05-03 JP JP2009510401A patent/JP5527758B2/en active Active
- 2007-05-03 WO PCT/EP2007/054321 patent/WO2007131891A1/en active Application Filing
- 2007-05-03 EP EP07728774.6A patent/EP2021440B1/en active Active
- 2007-05-03 CN CN2007800218086A patent/CN101466818B/en active Active
- 2007-05-03 US US12/300,882 patent/US20090186789A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JP5527758B2 (en) | 2014-06-25 |
| JP2009537642A (en) | 2009-10-29 |
| WO2007131891A1 (en) | 2007-11-22 |
| US20090186789A1 (en) | 2009-07-23 |
| EP2021440A1 (en) | 2009-02-11 |
| CN101466818A (en) | 2009-06-24 |
| CN101466818B (en) | 2013-03-27 |
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