CA2611649A1 - Oxidative stable oil formulation - Google Patents
Oxidative stable oil formulation Download PDFInfo
- Publication number
- CA2611649A1 CA2611649A1 CA002611649A CA2611649A CA2611649A1 CA 2611649 A1 CA2611649 A1 CA 2611649A1 CA 002611649 A CA002611649 A CA 002611649A CA 2611649 A CA2611649 A CA 2611649A CA 2611649 A1 CA2611649 A1 CA 2611649A1
- Authority
- CA
- Canada
- Prior art keywords
- base oil
- formulation according
- oil
- formulation
- derived
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 129
- 238000009472 formulation Methods 0.000 title claims abstract description 77
- 230000001590 oxidative effect Effects 0.000 title description 10
- 239000002199 base oil Substances 0.000 claims abstract description 128
- 239000003921 oil Substances 0.000 claims abstract description 102
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 27
- 239000011707 mineral Substances 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000005864 Sulphur Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000007866 anti-wear additive Substances 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- -1 benzotriazole compound Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 235000006708 antioxidants Nutrition 0.000 claims description 15
- 239000004927 clay Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 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 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000008116 organic polysulfides Chemical class 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000011959 amorphous silica alumina Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229920001021 polysulfide Polymers 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012208 gear oil Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 210000002741 palatine tonsil Anatomy 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- ZQMPWXFHAUDENN-UHFFFAOYSA-N 1,2-bis[(2-methylphenyl)amino]ethane Natural products CC1=CC=CC=C1NCCNC1=CC=CC=C1C ZQMPWXFHAUDENN-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- GAYUSSOCODCSNF-UHFFFAOYSA-N 1-(dodecyldisulfanyl)dodecane Chemical compound CCCCCCCCCCCCSSCCCCCCCCCCCC GAYUSSOCODCSNF-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- SKHBJDDIGYYYMJ-UHFFFAOYSA-N 2,6-ditert-butyl-6-methylcyclohexa-1,3-dien-1-ol Chemical compound CC(C)(C)C1=C(O)C(C)(C(C)(C)C)CC=C1 SKHBJDDIGYYYMJ-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001657 ferrierite group Inorganic materials 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- JUHXTONDLXIGGK-UHFFFAOYSA-N 1-n,4-n-bis(5-methylheptan-3-yl)benzene-1,4-diamine Chemical compound CCC(C)CC(CC)NC1=CC=C(NC(CC)CC(C)CC)C=C1 JUHXTONDLXIGGK-UHFFFAOYSA-N 0.000 description 1
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 description 1
- BJLNXEQCTFMBTH-UHFFFAOYSA-N 1-n,4-n-di(butan-2-yl)-1-n,4-n-dimethylbenzene-1,4-diamine Chemical compound CCC(C)N(C)C1=CC=C(N(C)C(C)CC)C=C1 BJLNXEQCTFMBTH-UHFFFAOYSA-N 0.000 description 1
- APTGHASZJUAUCP-UHFFFAOYSA-N 1-n,4-n-di(octan-2-yl)benzene-1,4-diamine Chemical compound CCCCCCC(C)NC1=CC=C(NC(C)CCCCCC)C=C1 APTGHASZJUAUCP-UHFFFAOYSA-N 0.000 description 1
- PWNBRRGFUVBTQG-UHFFFAOYSA-N 1-n,4-n-di(propan-2-yl)benzene-1,4-diamine Chemical compound CC(C)NC1=CC=C(NC(C)C)C=C1 PWNBRRGFUVBTQG-UHFFFAOYSA-N 0.000 description 1
- AIMXDOGPMWDCDF-UHFFFAOYSA-N 1-n,4-n-dicyclohexylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1CCCCC1 AIMXDOGPMWDCDF-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- GFVSLJXVNAYUJE-UHFFFAOYSA-N 10-prop-2-enylphenothiazine Chemical compound C1=CC=C2N(CC=C)C3=CC=CC=C3SC2=C1 GFVSLJXVNAYUJE-UHFFFAOYSA-N 0.000 description 1
- LXWZXEJDKYWBOW-UHFFFAOYSA-N 2,4-ditert-butyl-6-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O LXWZXEJDKYWBOW-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-UHFFFAOYSA-N 0.000 description 1
- VWDQJRIVNZKHKQ-UHFFFAOYSA-N 2-(3-aminoprop-1-enyl)phenol Chemical compound NCC=CC1=CC=CC=C1O VWDQJRIVNZKHKQ-UHFFFAOYSA-N 0.000 description 1
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 1
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 1
- RWYIKYWUOWLWHZ-UHFFFAOYSA-N 3,3-dimethyl-2,4-dihydro-1,4-benzothiazine Chemical compound C1=CC=C2NC(C)(C)CSC2=C1 RWYIKYWUOWLWHZ-UHFFFAOYSA-N 0.000 description 1
- VZXJHQBFMJESBV-UHFFFAOYSA-N 3,7-bis(2,4,4-trimethylpentan-2-yl)-10h-phenothiazine Chemical compound C1=C(C(C)(C)CC(C)(C)C)C=C2SC3=CC(C(C)(C)CC(C)(C)C)=CC=C3NC2=C1 VZXJHQBFMJESBV-UHFFFAOYSA-N 0.000 description 1
- HLFQEOHPFTVZLO-UHFFFAOYSA-N 3-methyl-2-(5-methyl-2H-triazol-4-yl)-N,N-dioctylaniline Chemical compound C(CCCCCCC)N(CCCCCCCC)C=1C(=C(C=CC=1)C)C=1N=NNC=1C HLFQEOHPFTVZLO-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- KCWYKOQNHLULEK-UHFFFAOYSA-N 4,5-diethyl-2h-benzotriazole Chemical compound CCC1=CC=C2NN=NC2=C1CC KCWYKOQNHLULEK-UHFFFAOYSA-N 0.000 description 1
- HXICLUNGKDYXRL-UHFFFAOYSA-N 4,5-dimethyl-2h-benzotriazole Chemical compound CC1=CC=C2NN=NC2=C1C HXICLUNGKDYXRL-UHFFFAOYSA-N 0.000 description 1
- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 description 1
- VAMBUGIXOVLJEA-UHFFFAOYSA-N 4-(butylamino)phenol Chemical compound CCCCNC1=CC=C(O)C=C1 VAMBUGIXOVLJEA-UHFFFAOYSA-N 0.000 description 1
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 description 1
- VCOONNWIINSFBA-UHFFFAOYSA-N 4-methoxy-n-(4-methoxyphenyl)aniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(OC)C=C1 VCOONNWIINSFBA-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- KZNDXCVEWRZEEU-UHFFFAOYSA-N 4-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1CCCCC1 KZNDXCVEWRZEEU-UHFFFAOYSA-N 0.000 description 1
- JQTYAZKTBXWQOM-UHFFFAOYSA-N 4-n-octan-2-yl-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CCCCCC)=CC=C1NC1=CC=CC=C1 JQTYAZKTBXWQOM-UHFFFAOYSA-N 0.000 description 1
- URFSURIOYABYBY-UHFFFAOYSA-N 5-ethyl-4-methyl-2h-benzotriazole Chemical compound CCC1=CC=C2NN=NC2=C1C URFSURIOYABYBY-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical class C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 241001248539 Eurema lisa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010710 diesel engine oil Substances 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
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- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 1
- JQMRSZJEVQNIPB-UHFFFAOYSA-N n,n'-diphenylpropane-1,3-diamine Chemical compound C=1C=CC=CC=1NCCCNC1=CC=CC=C1 JQMRSZJEVQNIPB-UHFFFAOYSA-N 0.000 description 1
- KESXDDATSRRGAH-UHFFFAOYSA-N n-(4-hydroxyphenyl)butanamide Chemical compound CCCC(=O)NC1=CC=C(O)C=C1 KESXDDATSRRGAH-UHFFFAOYSA-N 0.000 description 1
- JVKWTDRHWOSRFT-UHFFFAOYSA-N n-(4-hydroxyphenyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NC1=CC=C(O)C=C1 JVKWTDRHWOSRFT-UHFFFAOYSA-N 0.000 description 1
- VQLURHRLTDWRLX-UHFFFAOYSA-N n-(4-hydroxyphenyl)nonanamide Chemical compound CCCCCCCCC(=O)NC1=CC=C(O)C=C1 VQLURHRLTDWRLX-UHFFFAOYSA-N 0.000 description 1
- YASWBJXTHOXPGK-UHFFFAOYSA-N n-(4-hydroxyphenyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC1=CC=C(O)C=C1 YASWBJXTHOXPGK-UHFFFAOYSA-N 0.000 description 1
- CVVFFUKULYKOJR-UHFFFAOYSA-N n-phenyl-4-propan-2-yloxyaniline Chemical compound C1=CC(OC(C)C)=CC=C1NC1=CC=CC=C1 CVVFFUKULYKOJR-UHFFFAOYSA-N 0.000 description 1
- NYLGUNUDTDWXQE-UHFFFAOYSA-N n-phenyl-n-prop-2-enylaniline Chemical compound C=1C=CC=CC=1N(CC=C)C1=CC=CC=C1 NYLGUNUDTDWXQE-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—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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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/083—Dibenzyl sulfide
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/17—Electric or magnetic purposes for electric contacts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Insulating Materials (AREA)
Abstract
Oxidation stable oil formulation comprising a base oil composition comprising a mineral-derived naphthenic base oil, a mineral -derived paraffinic base oil, and/or a Fischer-Tropsch derived paraffinic base oil, a copper passivator and at most 0.1 wt% of an organic sulphur or phosphorus anti-wear additive.
Description
OXIDATIVE STABLE OIL FORMULATION
Field of invention The invention is related to an oxidation stable oil formulation comprising a base oil composition and additives.
Background of the invention US-A-6790386 describes a dielectric fluid comprising an iso-paraffin base oil and additives. The iso-paraffin base oil is prepared by hydrotreating, hydroisomerisation and hydrogenation of a paraffinic vacuum feedstock.
US-A-6214776 describes a formulation comprising a paraffinic base oil and an additive package containing a hindered phenol antioxidant and a metal deactivator, for use as load tap changer or transformer oil. According to this publication, base oils having a kinematic viscosity at 40 C of between 5 and 20 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
US-A-5241003 discloses a combination of a sulfur-containing antiwear additive and a carboxylic derivative dispersant for use as additive package for lubricants.
US-A-5773391 describes a composition comprising a polyol ester base oil, an aliphatic monocarboxylic acid mixture, and an additive package comprising an antioxidant and a metal deactivator. The document further discloses phosphorodithionates as antiwear additives.
WO-A-02070629 describes a process to make iso-paraffinic base oils from a wax as made in a Fischer-Tropsch process. According to this publication base oils having a kinematic viscosity at 100 C of between 2 and 9 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
US-A-5912212 describes oxidative stable oil lubricating formulations consisting of a hydrocracked paraffinic mineral base oil and 0.1 to 5 wto of a sulphur or phosphorus containing compound. In the examples a formulation consisting of a base oil and 3-methyl-5-tert-butyl-4-hydroxy propionic acid ester, dioctylamino-methyltolyltriazole and 0.4 wt% of dilaurylthio-dipropionate. The oil had a high oxidative stability.
A demand is acknowledged for high oxidation resistant oil products for use as for example electrical oil, in particular as a transformer oil or a switch gear oil, preferably without high additive treat rates due to adverse effects on other properties than oxidation stability.
Summary of the invention This aim is achieved with the following oil formulation. Oxidation stable oil formulation comprising a base oil composition comprising a mineral-derived naphthenic base oil, a mineral-derived paraffinic base oil, and/or a Fischer-Tropsch derived base oil, a copper passivator and of from 0.001 to less than 0.1 wt% of an organic sulphur or phosphorus based compound.
Applicants found that an oil formulation is achieved having a very high oxidation stability, however not requiring a high treat rate.
Brief description of the drawings Figure 1 and 2 represent the carbon distribution of two Fischer-Tropsch derived base oils as used in the examples.
Field of invention The invention is related to an oxidation stable oil formulation comprising a base oil composition and additives.
Background of the invention US-A-6790386 describes a dielectric fluid comprising an iso-paraffin base oil and additives. The iso-paraffin base oil is prepared by hydrotreating, hydroisomerisation and hydrogenation of a paraffinic vacuum feedstock.
US-A-6214776 describes a formulation comprising a paraffinic base oil and an additive package containing a hindered phenol antioxidant and a metal deactivator, for use as load tap changer or transformer oil. According to this publication, base oils having a kinematic viscosity at 40 C of between 5 and 20 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
US-A-5241003 discloses a combination of a sulfur-containing antiwear additive and a carboxylic derivative dispersant for use as additive package for lubricants.
US-A-5773391 describes a composition comprising a polyol ester base oil, an aliphatic monocarboxylic acid mixture, and an additive package comprising an antioxidant and a metal deactivator. The document further discloses phosphorodithionates as antiwear additives.
WO-A-02070629 describes a process to make iso-paraffinic base oils from a wax as made in a Fischer-Tropsch process. According to this publication base oils having a kinematic viscosity at 100 C of between 2 and 9 cSt can be used as base oil in formulations such as electrical oils or transformer oils.
US-A-5912212 describes oxidative stable oil lubricating formulations consisting of a hydrocracked paraffinic mineral base oil and 0.1 to 5 wto of a sulphur or phosphorus containing compound. In the examples a formulation consisting of a base oil and 3-methyl-5-tert-butyl-4-hydroxy propionic acid ester, dioctylamino-methyltolyltriazole and 0.4 wt% of dilaurylthio-dipropionate. The oil had a high oxidative stability.
A demand is acknowledged for high oxidation resistant oil products for use as for example electrical oil, in particular as a transformer oil or a switch gear oil, preferably without high additive treat rates due to adverse effects on other properties than oxidation stability.
Summary of the invention This aim is achieved with the following oil formulation. Oxidation stable oil formulation comprising a base oil composition comprising a mineral-derived naphthenic base oil, a mineral-derived paraffinic base oil, and/or a Fischer-Tropsch derived base oil, a copper passivator and of from 0.001 to less than 0.1 wt% of an organic sulphur or phosphorus based compound.
Applicants found that an oil formulation is achieved having a very high oxidation stability, however not requiring a high treat rate.
Brief description of the drawings Figure 1 and 2 represent the carbon distribution of two Fischer-Tropsch derived base oils as used in the examples.
Detailed description of the invention Applicants found that when a mineral-derived base oil of the so-called paraffinic type or naphthenic type, and/or a Fischer-Tropsch derived base oil is combined with at least one copper passivator and a low content of an anti-wear additive, an oil product is obtained which has properties highly suitable for use as an electrical oil. It was not to be expected that the combination of the copper passivator and a small amount of an anti-wear additive would result in such an improvement in oxidative stability. A mineral-derived base oil has the meaning within the context of this specification that the base oil was obtained from a mineral oil source, while a Fischer-Tropsch derived base oil was derived from Fischer-Tropsch synthesis products.
Organic sulphur or phosphorus based compounds preferably are sulphur and phosphorus containing compounds such as sulfides, phosphides, dithiophopsphates and dithiocarbamates. More preferably, sulphur and phosphorus containing compounds are used which are known to be used as an anti-wear additive in lubricating oil formulations. Yet more preferably an organic polysulphide compound is used. With polysulfide is here meant that the organic compound comprises at least one group where two sulphur atoms are directly linked. A preferred polysulfide compound is a disulfide compound. Preferred polysulfide compounds are represented by the formula (I) Rl- (S) a-R2 (I) wherein:
a is 2, 3, 4 or 5, preferably 2;
R1 and R2 may be the same or different and each may be straight or branched alkyl group of 1 to 22 carbon atoms, aryl groups of 6-20 carbon atoms, alkylaryl groups of 7-20 carbon atoms or arylalkyl groups of 7-20 carbon atoms. Preferred are arylalkyl groups, more preferred are optionally substituted benzyl groups. More preferably R1 and R2 are independently selected from a benzyl group or a straight or branched dodecyl group. Examples of possible sulphur and phosphorus containing compounds and the preferred compounds mentioned here are described in the aforementioned US-A-5912212 as its component (b), which publication is incorporated by reference. Examples of suitable disulfide compounds are dibenzyldi-sulfide,ditertdodecyldisulfide and didodecyldisulfide.
The content of the organic sulphur or phosphorus anti-wear additive in the oil formulation is preferably less than formulation 800 mg/kg and even more preferably less than 400 mg/kg. The lower limit is preferably 1 mg/kg more preferably 10 mg/kg, most preferably 50 mg/kg.
The copper passivator or electrostatic discharge depressant, sometimes also referred as metal deactivator, may be the typical copper passivator of which N-salicylideneethylamine, N,N'-di salicylideneethyl-diamine, triethylenediamine, ethylenediamminetetraacetic acid, phosphoric acid, citric acid and gluconic acid.
More preferred are lecithin, thiadiazole, imidazole and pyrazole and derivates thereof. Even more preferred are zinc dialkyldithiophosphates, dialkyldithiocarbamates and benzotriazoles and their tetrahydroderivates. Most preferred are the compounds according to formula (II) or even more preferred the optionally substituted benzotriazole compound represented by the formula (III) C4tt- N
(II) ~ c N
(III) wherein R4 may be hydrogen or a group represented by the formula (IV) ~.~
(IV) or by the formula (V) (V) wherein:
Organic sulphur or phosphorus based compounds preferably are sulphur and phosphorus containing compounds such as sulfides, phosphides, dithiophopsphates and dithiocarbamates. More preferably, sulphur and phosphorus containing compounds are used which are known to be used as an anti-wear additive in lubricating oil formulations. Yet more preferably an organic polysulphide compound is used. With polysulfide is here meant that the organic compound comprises at least one group where two sulphur atoms are directly linked. A preferred polysulfide compound is a disulfide compound. Preferred polysulfide compounds are represented by the formula (I) Rl- (S) a-R2 (I) wherein:
a is 2, 3, 4 or 5, preferably 2;
R1 and R2 may be the same or different and each may be straight or branched alkyl group of 1 to 22 carbon atoms, aryl groups of 6-20 carbon atoms, alkylaryl groups of 7-20 carbon atoms or arylalkyl groups of 7-20 carbon atoms. Preferred are arylalkyl groups, more preferred are optionally substituted benzyl groups. More preferably R1 and R2 are independently selected from a benzyl group or a straight or branched dodecyl group. Examples of possible sulphur and phosphorus containing compounds and the preferred compounds mentioned here are described in the aforementioned US-A-5912212 as its component (b), which publication is incorporated by reference. Examples of suitable disulfide compounds are dibenzyldi-sulfide,ditertdodecyldisulfide and didodecyldisulfide.
The content of the organic sulphur or phosphorus anti-wear additive in the oil formulation is preferably less than formulation 800 mg/kg and even more preferably less than 400 mg/kg. The lower limit is preferably 1 mg/kg more preferably 10 mg/kg, most preferably 50 mg/kg.
The copper passivator or electrostatic discharge depressant, sometimes also referred as metal deactivator, may be the typical copper passivator of which N-salicylideneethylamine, N,N'-di salicylideneethyl-diamine, triethylenediamine, ethylenediamminetetraacetic acid, phosphoric acid, citric acid and gluconic acid.
More preferred are lecithin, thiadiazole, imidazole and pyrazole and derivates thereof. Even more preferred are zinc dialkyldithiophosphates, dialkyldithiocarbamates and benzotriazoles and their tetrahydroderivates. Most preferred are the compounds according to formula (II) or even more preferred the optionally substituted benzotriazole compound represented by the formula (III) C4tt- N
(II) ~ c N
(III) wherein R4 may be hydrogen or a group represented by the formula (IV) ~.~
(IV) or by the formula (V) (V) wherein:
5 c is 0, 1, 2 or 3;
R3 is a straight or branched C1-4 alkyl group. Preferably R3 is methyl or ethyl and C is 1 or 2. R5 is a methylene or ethylene group; R6 and R7 are hydrogen or the same or different straight or branched alkyl groups of 1-18 carbon atoms, preferably a branched alkyl group of 1-12 carbon atoms; R8 and R9 are the same or different alkyl groups of 3-15 carbon atoms, preferably of 4-9 carbon atoms.
R3 is a straight or branched C1-4 alkyl group. Preferably R3 is methyl or ethyl and C is 1 or 2. R5 is a methylene or ethylene group; R6 and R7 are hydrogen or the same or different straight or branched alkyl groups of 1-18 carbon atoms, preferably a branched alkyl group of 1-12 carbon atoms; R8 and R9 are the same or different alkyl groups of 3-15 carbon atoms, preferably of 4-9 carbon atoms.
Preferred compounds are 1-[bis(2-ethylhexyl)-aminomethyl]benzotriazole, methylbenzotriazole, dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethylbenzotriazole and mixtures thereof. Other preferred compounds include (N-Bis(2-ethylhexyl)-aminomethyl-tolutriazole, non-substituted benzotriazole, and 5-methyl-lH-benzotriazole.
Examples of copper passivator additives as described above are described in US-A-5912212, EP-A-1054052 and in US-A-2002/0109127, which publications are hereby incorporated by reference. These benzotriazoles compounds are preferred because they also act as an electrostatic discharge depressant, which is beneficial when the oil formulation is used as an electrical oil. Copper passivator additives as those described above are commercially available under the product names BTA, TTA, IRGAMET 39, IRGAMET30 and IRGAMET 38S from CIBA Ltd Basel Switzerland, also traded under the trade name Reomet by CIBA.
The content of the above copper passivator in the oil formulation is preferably above 1 mg/kg and more preferably above 5 mg/kg. A practical upper limit may vary depending on the specific application of the oil formulation. For example, when desiring improved dielectric discharge tendencies of the oil for use as electrical oil it may be desired to add a high concentration of the copper passivator additive. This concentration may be up to 3 wt%, preferably however in the range of from 0.001 to 1 wto. Applicants found that the advantages of the invention can be achieved at concentrations below 1000 mg/kg and more preferably below 300 mg/kg, even more preferably below 50 mg/kg.
Examples of copper passivator additives as described above are described in US-A-5912212, EP-A-1054052 and in US-A-2002/0109127, which publications are hereby incorporated by reference. These benzotriazoles compounds are preferred because they also act as an electrostatic discharge depressant, which is beneficial when the oil formulation is used as an electrical oil. Copper passivator additives as those described above are commercially available under the product names BTA, TTA, IRGAMET 39, IRGAMET30 and IRGAMET 38S from CIBA Ltd Basel Switzerland, also traded under the trade name Reomet by CIBA.
The content of the above copper passivator in the oil formulation is preferably above 1 mg/kg and more preferably above 5 mg/kg. A practical upper limit may vary depending on the specific application of the oil formulation. For example, when desiring improved dielectric discharge tendencies of the oil for use as electrical oil it may be desired to add a high concentration of the copper passivator additive. This concentration may be up to 3 wt%, preferably however in the range of from 0.001 to 1 wto. Applicants found that the advantages of the invention can be achieved at concentrations below 1000 mg/kg and more preferably below 300 mg/kg, even more preferably below 50 mg/kg.
The oil formulation preferably also comprises an anti-oxidant additive. It has been found that, especially in case the base oil is a mineral paraffinic base oil or a Fischer-Tropsch derived base oil, the sludge formed and total acidity both measured after the IEC 61125 C
oxidation test, which properties are indicators for good oxidation stable oils, are considerably reduced when also an anti-oxidant is present. The anti-oxidant may be a so-called hindered phenolic or amine antioxidant, for example naphthols, sterically hindered monohydric, dihydric and trihydric phenols, sterically hindered dinuclear, trinuclear and polynuclear phenols, alkylated or styrenated diphenylamines or ionol derived hindered phenols. Sterically hindered phenolic antioxidants of particular interest are selected from the group consisting of 2,6-di-tert-butylphenol (IRGANOX TM L 140, CIBA), di tert-butylated hydroxotoluene (BHT), methylene-4,4'-bis-(2.6-tert-butylphenol), 2,2'-methylene bis-(4,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-hydroxyhydrocinnamate) (IRGANOX TM L109, CIBA), ((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)thio) acetic acid, C10-C14isoalkyl esters (IRGANOX TM L118, CIBA), 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9alkyl esters (IRGANOX TM L135, CIBA,) tetrakis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl)methane (IRGANOX TM 1010, CIBA), thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (IRGANOX TM 1035, CIBA), octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (IRGANOX TM 1076, CIBA) and 2,5-di-tert-butylhydroquinone. These products are known and are commercially available. Of most particular interest is 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid-C7-C9-alkyl ester.
oxidation test, which properties are indicators for good oxidation stable oils, are considerably reduced when also an anti-oxidant is present. The anti-oxidant may be a so-called hindered phenolic or amine antioxidant, for example naphthols, sterically hindered monohydric, dihydric and trihydric phenols, sterically hindered dinuclear, trinuclear and polynuclear phenols, alkylated or styrenated diphenylamines or ionol derived hindered phenols. Sterically hindered phenolic antioxidants of particular interest are selected from the group consisting of 2,6-di-tert-butylphenol (IRGANOX TM L 140, CIBA), di tert-butylated hydroxotoluene (BHT), methylene-4,4'-bis-(2.6-tert-butylphenol), 2,2'-methylene bis-(4,6-di-tert-butylphenol), 1,6-hexamethylene-bis-(3,5-di-tert-butyl-hydroxyhydrocinnamate) (IRGANOX TM L109, CIBA), ((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)thio) acetic acid, C10-C14isoalkyl esters (IRGANOX TM L118, CIBA), 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9alkyl esters (IRGANOX TM L135, CIBA,) tetrakis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl)methane (IRGANOX TM 1010, CIBA), thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (IRGANOX TM 1035, CIBA), octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (IRGANOX TM 1076, CIBA) and 2,5-di-tert-butylhydroquinone. These products are known and are commercially available. Of most particular interest is 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid-C7-C9-alkyl ester.
Examples of amine antioxidants are aromatic amine anti-oxidants for example N,N'-Di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine, N,N'-bis(l-ethyl-3-methyl-pentyl)-p-phenylene-diamine, N,N'-bis(1-methyl-heptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylene-diamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(naphthyl-2-)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N'-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluene-sulfoamido)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-l-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethyl-aminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di(phenylamino)ethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,3-di-(phenylamino)propane, (o-tolyl)biguanide, di[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-l-naphthylamine, mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine, tert-octylated phenothiazine, 3,7-di-tert-octylphenothiazine. Also possible amine antioxidants are those according to formula VIII and IX
of EP-A-1054052, which compounds are also described in US-A-4,824,601, which publications are hereby incorporated by reference.
The content of the anti oxidant additive is preferably less than 2 wt% and more preferably less than 1 wto. The content is preferably less than 0,6 wta in certain applications, such as when the oil formulation is used as an electrical oil. The content of antioxidant is preferably greater than 10 mg/kg.
The oil formulation preferably has a sulphur content of below 0,5 wt% and even more preferably below 0,15 wt%.
The source of the majority of the sulphur in the oil formulation will be the sulphur as contained in the base oil component of the oil formulation according the invention.
The base oil composition preferably has a kinematic viscosity at 100 C of less than 50 mm2/sec, more preferably between 2 and 25 mm2/sec, most preferably between 2 and 15 mm2/sec. The base oil composition preferably has a kinematic viscosity at 40 C of between 1 and 200 mm2/sec, more preferably between 3.5 and 100 mm2/sec, most preferably between 5 and 12 mm2/sec. The viscosity of the base oil composition will also depend on the particular use of the oil formulation. If the oil formulation is used as an electrical oil its kinematic viscosity at 40 Cis preferably between 1 and 50 mm2/sec.
More preferably, if this electrical oil formulation is a transformer oil, the base oil will preferably have a kinematic viscosity at 40 C of between 5 and 15 mm2/sec.
If the electrical oil is a low temperature switch gear oil the base oil viscosity at 40 C is preferably between 1 and 15 and more preferably between 1 and 4 mm2/sec.
The flash point of the base oil composition as measured by ASTM D92 may be greater than 90 C, preferably greater than 120 C, yet more preferably greater than 140 C, and even more preferably greater 5 than 170 C. The higher flash points are desirable for applications where peak temperatures can exceed the average oil temperature, for instance in applications under high temperature and/or with restricted heat transmission potential. Examples are electric 10 transformers and electric engines.
The base oil composition may comprise one or more base oils selected from mineral-derived naphthenic base oils, mineral-derived paraffic base oils, or Fischer-Tropsch derived base oils.
The base oil composition may this comprise a mineral-derived base oil of the so-called paraffinic type or naphthenic type. Such base oils are obtained by refinery processes starting from paraffinic and naphthenic crude feeds. Mineral-derived naphthenic base oils for the purpose of this invention are defined as having a pour point of below -20 C and a viscosity index of below 70.
Mineral-derived paraffin base oils are defined by a viscosity index of greater than 70, preferably greater than 90. Mineral-derived naphthenic and paraffin base oils are well known and described in more detail in "Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN
0-8247-9256-4, pages 28-35.
Applicants found that very good oxidative stable oil formulations can be obtained when the base oil composition has a saturates content as measured by IP386 of preferably greater than 98 wt%, more preferably greater than 99 wt% and even more preferably greater than 99.5 wt% as measured on fresh base oil.
The base oil composition preferably comprises a base oil comprising a series of iso-paraffins having n, n+l, n+2, n+3 and n+4 carbon atoms and wherein n is a number between 20 and 35.
Preferably, the paraffin content in the base oil composition is greater than 80 wt%, more preferably greater than 90 wt%, yet more preferably greater than 95%, and again more preferably greater than 98%.
The base oil composition furthermore may preferably have a content of naphthenic compounds of between 1 and wto. It has been found that these base oils have a good additive response to the additives listed above when 15 aiming to improve oxidation stability. The content of naphthenic compounds and the presence of such a continuous series of iso-paraffins may be measured by Field desorption/Field Ionisation (FD/FI) technique. In this technique the oil sample is first separated into a 20 polar (aromatic) phase and a non-polar (saturates) phase by making use of a high performance liquid chromatography (HPLC) method IP368/01, wherein as mobile phase pentane is used instead of hexane as the method states. The saturates and aromatic fractions are then analyzed using a Finnigan MAT90 mass spectrometer equipped with a Field desorption/Field Ionisation (FD/FI) interface, wherein FI
(a "soft" ionisation technique) is used for the determination of hydrocarbon types in terms of carbon number and hydrogen deficiency. The type classification of compounds in mass spectrometry is determined by the characteristic ions formed and is normally classified by "z number". This is given by the general formula for all hydrocarbon species: CnH2n+z= Because the saturates phase is analysed separately from the aromatic phase it is possible to determine the content of the different iso-paraffins having the same stoichiometry or n-number. The results of the mass spectrometer are processed using commercial software (poly 32; available from Sierra Analytics LLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA) to determine the relative proportions of each hydrocarbon type.
The base oil composition having the continuous iso-paraffinic series as described above are preferably obtained by hydroisomerisation of a paraffinic wax, yet more preferably followed by some type of dewaxing, such as solvent or catalytic dewaxing.
The above described base oil composition may preferably be obtained by hydroisomerisation of a paraffinic wax, preferably followed by a dewaxing treatment, such as a solvent or catalytic dewaxing treatment. The paraffinic wax may be a highly paraffinic slack wax. More preferably the paraffinic wax is a Fischer-Tropsch derived wax, because of its purity and even higher paraffinic content.
The base oils as derived from a Fischer-Tropsch wax as here described will be referred to in this description as Fischer-Tropsch derived base oils.
Examples of Fischer-Tropsch processes which for example can be used to prepare the above-described Fischer-Tropsch derived base oil are the so-called commercial Slurry Phase Distillate technology of Sasol, the Shell Middle Distillate Synthesis Process and the "AGC-21" Exxon Mobil process. These and other processes are for example described in more detail in EP-A-776959, EP-A-668342, US-A-4943672, US-A-5059299, WO-A-9934917 and WO-A-9920720. Typically these Fischer-Tropsch synthesis products will comprise hydrocarbons having 1 to 100 and even more than 100 carbon atoms. This hydrocarbon product will comprise normal paraffins, iso-paraffins, oxygenated products and unsaturated products. If base oils are one of the desired iso-paraffinic products it may be advantageous to use a relatively heavy Fischer-Tropsch derived feed. The relatively heavy Fischer-Tropsch derived feed has at least 30 wto, preferably at least 50 wto, and more preferably at least 55 wt% of compounds having at least 30 carbon atoms. Furthermore the weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms of the Fischer-Tropsch derived feed is preferably at least 0.2, more preferably at least 0.4 and most preferably at least 0.55. Preferably the Fischer-Tropsch derived feed comprises a C20+ fraction having an ASF-alpha value (Anderson-Schulz-Flory chain growth factor) of at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955. Such a Fischer-Tropsch derived feed can be obtained by any process, which yields a relatively heavy Fischer-Tropsch product as described above. Not all Fischer-Tropsch processes yield such a heavy product. An example of a suitable Fischer-Tropsch process is described in WO-A-9934917.
The Fischer-Tropsch derived product will contain no or very little sulphur and nitrogen containing compounds.
This is typical for a product derived from a Fischer-Tropsch reaction, which uses synthesis gas containing almost no impurities. Sulphur and nitrogen levels will generally be below the detection limits, which are currently 5 mg/kg for sulphur and 1 mg/kg for nitrogen respectively.
The content of the anti oxidant additive is preferably less than 2 wt% and more preferably less than 1 wto. The content is preferably less than 0,6 wta in certain applications, such as when the oil formulation is used as an electrical oil. The content of antioxidant is preferably greater than 10 mg/kg.
The oil formulation preferably has a sulphur content of below 0,5 wt% and even more preferably below 0,15 wt%.
The source of the majority of the sulphur in the oil formulation will be the sulphur as contained in the base oil component of the oil formulation according the invention.
The base oil composition preferably has a kinematic viscosity at 100 C of less than 50 mm2/sec, more preferably between 2 and 25 mm2/sec, most preferably between 2 and 15 mm2/sec. The base oil composition preferably has a kinematic viscosity at 40 C of between 1 and 200 mm2/sec, more preferably between 3.5 and 100 mm2/sec, most preferably between 5 and 12 mm2/sec. The viscosity of the base oil composition will also depend on the particular use of the oil formulation. If the oil formulation is used as an electrical oil its kinematic viscosity at 40 Cis preferably between 1 and 50 mm2/sec.
More preferably, if this electrical oil formulation is a transformer oil, the base oil will preferably have a kinematic viscosity at 40 C of between 5 and 15 mm2/sec.
If the electrical oil is a low temperature switch gear oil the base oil viscosity at 40 C is preferably between 1 and 15 and more preferably between 1 and 4 mm2/sec.
The flash point of the base oil composition as measured by ASTM D92 may be greater than 90 C, preferably greater than 120 C, yet more preferably greater than 140 C, and even more preferably greater 5 than 170 C. The higher flash points are desirable for applications where peak temperatures can exceed the average oil temperature, for instance in applications under high temperature and/or with restricted heat transmission potential. Examples are electric 10 transformers and electric engines.
The base oil composition may comprise one or more base oils selected from mineral-derived naphthenic base oils, mineral-derived paraffic base oils, or Fischer-Tropsch derived base oils.
The base oil composition may this comprise a mineral-derived base oil of the so-called paraffinic type or naphthenic type. Such base oils are obtained by refinery processes starting from paraffinic and naphthenic crude feeds. Mineral-derived naphthenic base oils for the purpose of this invention are defined as having a pour point of below -20 C and a viscosity index of below 70.
Mineral-derived paraffin base oils are defined by a viscosity index of greater than 70, preferably greater than 90. Mineral-derived naphthenic and paraffin base oils are well known and described in more detail in "Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN
0-8247-9256-4, pages 28-35.
Applicants found that very good oxidative stable oil formulations can be obtained when the base oil composition has a saturates content as measured by IP386 of preferably greater than 98 wt%, more preferably greater than 99 wt% and even more preferably greater than 99.5 wt% as measured on fresh base oil.
The base oil composition preferably comprises a base oil comprising a series of iso-paraffins having n, n+l, n+2, n+3 and n+4 carbon atoms and wherein n is a number between 20 and 35.
Preferably, the paraffin content in the base oil composition is greater than 80 wt%, more preferably greater than 90 wt%, yet more preferably greater than 95%, and again more preferably greater than 98%.
The base oil composition furthermore may preferably have a content of naphthenic compounds of between 1 and wto. It has been found that these base oils have a good additive response to the additives listed above when 15 aiming to improve oxidation stability. The content of naphthenic compounds and the presence of such a continuous series of iso-paraffins may be measured by Field desorption/Field Ionisation (FD/FI) technique. In this technique the oil sample is first separated into a 20 polar (aromatic) phase and a non-polar (saturates) phase by making use of a high performance liquid chromatography (HPLC) method IP368/01, wherein as mobile phase pentane is used instead of hexane as the method states. The saturates and aromatic fractions are then analyzed using a Finnigan MAT90 mass spectrometer equipped with a Field desorption/Field Ionisation (FD/FI) interface, wherein FI
(a "soft" ionisation technique) is used for the determination of hydrocarbon types in terms of carbon number and hydrogen deficiency. The type classification of compounds in mass spectrometry is determined by the characteristic ions formed and is normally classified by "z number". This is given by the general formula for all hydrocarbon species: CnH2n+z= Because the saturates phase is analysed separately from the aromatic phase it is possible to determine the content of the different iso-paraffins having the same stoichiometry or n-number. The results of the mass spectrometer are processed using commercial software (poly 32; available from Sierra Analytics LLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA) to determine the relative proportions of each hydrocarbon type.
The base oil composition having the continuous iso-paraffinic series as described above are preferably obtained by hydroisomerisation of a paraffinic wax, yet more preferably followed by some type of dewaxing, such as solvent or catalytic dewaxing.
The above described base oil composition may preferably be obtained by hydroisomerisation of a paraffinic wax, preferably followed by a dewaxing treatment, such as a solvent or catalytic dewaxing treatment. The paraffinic wax may be a highly paraffinic slack wax. More preferably the paraffinic wax is a Fischer-Tropsch derived wax, because of its purity and even higher paraffinic content.
The base oils as derived from a Fischer-Tropsch wax as here described will be referred to in this description as Fischer-Tropsch derived base oils.
Examples of Fischer-Tropsch processes which for example can be used to prepare the above-described Fischer-Tropsch derived base oil are the so-called commercial Slurry Phase Distillate technology of Sasol, the Shell Middle Distillate Synthesis Process and the "AGC-21" Exxon Mobil process. These and other processes are for example described in more detail in EP-A-776959, EP-A-668342, US-A-4943672, US-A-5059299, WO-A-9934917 and WO-A-9920720. Typically these Fischer-Tropsch synthesis products will comprise hydrocarbons having 1 to 100 and even more than 100 carbon atoms. This hydrocarbon product will comprise normal paraffins, iso-paraffins, oxygenated products and unsaturated products. If base oils are one of the desired iso-paraffinic products it may be advantageous to use a relatively heavy Fischer-Tropsch derived feed. The relatively heavy Fischer-Tropsch derived feed has at least 30 wto, preferably at least 50 wto, and more preferably at least 55 wt% of compounds having at least 30 carbon atoms. Furthermore the weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms of the Fischer-Tropsch derived feed is preferably at least 0.2, more preferably at least 0.4 and most preferably at least 0.55. Preferably the Fischer-Tropsch derived feed comprises a C20+ fraction having an ASF-alpha value (Anderson-Schulz-Flory chain growth factor) of at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955. Such a Fischer-Tropsch derived feed can be obtained by any process, which yields a relatively heavy Fischer-Tropsch product as described above. Not all Fischer-Tropsch processes yield such a heavy product. An example of a suitable Fischer-Tropsch process is described in WO-A-9934917.
The Fischer-Tropsch derived product will contain no or very little sulphur and nitrogen containing compounds.
This is typical for a product derived from a Fischer-Tropsch reaction, which uses synthesis gas containing almost no impurities. Sulphur and nitrogen levels will generally be below the detection limits, which are currently 5 mg/kg for sulphur and 1 mg/kg for nitrogen respectively.
The process will generally comprise a Fischer-Tropsch synthesis, a hydroisomerisation step and an optional pour point reducing step, wherein said hydroisomerisation step and optional pour point reducing step are performed as:
(a) hydrocracking/hydroisomerisating a Fischer-Tropsch product, (b) separating the product of step (a) into at least one or more distillate fuel fractions and a base oil or base oil intermediate fraction.
If the viscosity and pour point of the base oil as obtained in step (b) is as desired no further processing is necessary and the oil can be used as the base oil according the invention. If required, the pour point of the base oil intermediate fraction is suitably further reduced in a step (c) by means of solvent or preferably catalytic dewaxing of the oil obtained in step (b) to obtain oil having the preferred low pour point. The desired viscosity of the base oil may be obtained by isolating by means of distillation from the intermediate base oil fraction or from the dewaxed oil the a suitable boiling range product corresponding with the desired viscosity. Distillation may be suitably a vacuum distillation step.
The hydroconversion/hydroisomerisation reaction of step (a) is preferably performed in the presence of hydrogen and a catalyst, which catalyst can be chosen from those known to one skilled in the art as being suitable for this reaction of which some will be described in more detail below. The catalyst may in principle be any catalyst known in the art to be suitable for isomerising paraffinic molecules. In general, suitable hydroconversion/hydroisomerisation catalysts are those comprising a hydrogenation component supported on a refractory oxide carrier, such as amorphous silica-alumina (ASA), alumina, fluorided alumina, molecular sieves (zeolites) or mixtures of two or more of these.
One type of preferred catalysts to be applied in the 5 hydroconversion/hydroisomerisation step in accordance with the present invention are hydroconversion/
hydroisomerisation catalysts comprising platinum and/or palladium as the hydrogenation component. A very much preferred hydroconversion/hydroisomerisation catalyst 10 comprises platinum and palladium supported on an amorphous silica-alumina (ASA) carrier. The platinum and/or palladium is suitably present in an amount of from 0.1 to 5.0% by weight, more suitably from 0.2 to 2.0% by weight, calculated as element and based on total weight 15 of carrier. If both present, the weight ratio of platinum to palladium may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5.
Examples of suitable noble metal on ASA catalysts are, for instance, disclosed in WO-A-9410264 and EP-A-0582347.
Other suitable noble metal-based catalysts, such as platinum on a fluorided alumina carrier, are disclosed in e.g. US-A-5059299 and WO-A-9220759.
A second type of suitable hydroconversion/
hydroisomerisation catalysts are those comprising at least one Group VIB metal, preferably tungsten and/or molybdenum, and at least one non-noble Group VIII metal, preferably nickel and/or cobalt, as the hydrogenation component. Both metals may be present as oxides, sulphides or a combination thereof. The Group VIB metal is suitably present in an amount of from 1 to 35% by weight, more suitably from 5 to 30% by weight, calculated as element and based on total weight of the carrier. The non-noble Group VIII metal is suitably present in an amount of from 1 to 25 wto, preferably 2 to 15 wto, calculated as element and based on total weight of carrier. A hydroconversion catalyst of this type, which has been found particularly suitable, is a catalyst comprising nickel and tungsten supported on fluorided alumina.
The above non-noble metal-based catalysts are preferably used in their sulphided form. In order to maintain the sulphided form of the catalyst during use some sulphur needs to be present in the feed. Preferably at least 10 mg/kg and more preferably between 50 and 150 mg/kg of sulphur is present in the feed.
A preferred catalyst, which can be used in a non-sulphided form, comprises a non-noble Group VIII metal, e.g., iron, nickel, in conjunction with a Group IB metal, e.g., copper, supported on an acidic support. Copper is preferably present to suppress hydrogenolysis of paraffins to methane. The catalyst has a pore volume preferably in the range of 0.35 to 1.10 ml/g as determined by water absorption, a surface area of preferably between 200-500 m2/g as determined by BET
nitrogen adsorption, and a bulk density of between 0.4-1.0 g/ml. The catalyst support is preferably made of an amorphous silica-alumina wherein the alumina may be present within wide range of between 5 and 96 wt%, preferably between 20 and 85 wto. The silica content as Si02 is preferably between 15 and 80 wt%. Also, the support may contain small amounts, e.g., 20-30 wto, of a binder, e.g., alumina, silica, Group IVA metal oxides, and various types of clays, magnesia, etc., preferably alumina or silica.
The preparation of amorphous silica-alumina microspheres has been described in Ryland, Lloyd B., Tamele, M.W., and Wilson, J.N., Cracking Catalysts, Catalysis: volume VII, Ed. Paul H. Emmett, Reinhold Publishing Corporation, New York, 1960, pp. 5-9.
The catalyst is prepared by co-impregnating the metals from solutions onto the support, drying at 100-150 C, and calcining in air at 200-550 C. The Group VIII metal is present in amounts of about 15 wt% or less, preferably 1-12 wt%, while the Group IB metal is usually present in lesser amounts, e.g., 1:2 to about 1:20 weight ratio respecting the Group VIII metal.
A typical catalyst is shown below:
Ni, wt% 2.5-3.5 Cu, wt% 0.25-0.35 A1203-Si02 wto 65-75 A1203 (binder) wto 25-30 Surface Area 290-325 m2/g Pore Volume (Hg) 0.35-0.45 ml/g Bulk Density 0.58-0.68 g/ml Another class of suitable hydroconversion/
hydroisomerisation catalysts are those based on zeolitic materials, suitably comprising at least one Group VIII
metal component, preferably Pt and/or Pd, as the hydrogenation component. Suitable zeolitic and other aluminosilicate materials, then, include Zeolite beta, Zeolite Y, Ultra Stable Y, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite, mordenite and silica-aluminophosphates, such as SAPO-11 and SAPO-31.
Examples of suitable hydroisomerisation/
hydroisomerisation catalysts are, for instance, described in WO-A-9201657. Combinations of these catalysts are also possible. Very suitable hydroconversion/
(a) hydrocracking/hydroisomerisating a Fischer-Tropsch product, (b) separating the product of step (a) into at least one or more distillate fuel fractions and a base oil or base oil intermediate fraction.
If the viscosity and pour point of the base oil as obtained in step (b) is as desired no further processing is necessary and the oil can be used as the base oil according the invention. If required, the pour point of the base oil intermediate fraction is suitably further reduced in a step (c) by means of solvent or preferably catalytic dewaxing of the oil obtained in step (b) to obtain oil having the preferred low pour point. The desired viscosity of the base oil may be obtained by isolating by means of distillation from the intermediate base oil fraction or from the dewaxed oil the a suitable boiling range product corresponding with the desired viscosity. Distillation may be suitably a vacuum distillation step.
The hydroconversion/hydroisomerisation reaction of step (a) is preferably performed in the presence of hydrogen and a catalyst, which catalyst can be chosen from those known to one skilled in the art as being suitable for this reaction of which some will be described in more detail below. The catalyst may in principle be any catalyst known in the art to be suitable for isomerising paraffinic molecules. In general, suitable hydroconversion/hydroisomerisation catalysts are those comprising a hydrogenation component supported on a refractory oxide carrier, such as amorphous silica-alumina (ASA), alumina, fluorided alumina, molecular sieves (zeolites) or mixtures of two or more of these.
One type of preferred catalysts to be applied in the 5 hydroconversion/hydroisomerisation step in accordance with the present invention are hydroconversion/
hydroisomerisation catalysts comprising platinum and/or palladium as the hydrogenation component. A very much preferred hydroconversion/hydroisomerisation catalyst 10 comprises platinum and palladium supported on an amorphous silica-alumina (ASA) carrier. The platinum and/or palladium is suitably present in an amount of from 0.1 to 5.0% by weight, more suitably from 0.2 to 2.0% by weight, calculated as element and based on total weight 15 of carrier. If both present, the weight ratio of platinum to palladium may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5.
Examples of suitable noble metal on ASA catalysts are, for instance, disclosed in WO-A-9410264 and EP-A-0582347.
Other suitable noble metal-based catalysts, such as platinum on a fluorided alumina carrier, are disclosed in e.g. US-A-5059299 and WO-A-9220759.
A second type of suitable hydroconversion/
hydroisomerisation catalysts are those comprising at least one Group VIB metal, preferably tungsten and/or molybdenum, and at least one non-noble Group VIII metal, preferably nickel and/or cobalt, as the hydrogenation component. Both metals may be present as oxides, sulphides or a combination thereof. The Group VIB metal is suitably present in an amount of from 1 to 35% by weight, more suitably from 5 to 30% by weight, calculated as element and based on total weight of the carrier. The non-noble Group VIII metal is suitably present in an amount of from 1 to 25 wto, preferably 2 to 15 wto, calculated as element and based on total weight of carrier. A hydroconversion catalyst of this type, which has been found particularly suitable, is a catalyst comprising nickel and tungsten supported on fluorided alumina.
The above non-noble metal-based catalysts are preferably used in their sulphided form. In order to maintain the sulphided form of the catalyst during use some sulphur needs to be present in the feed. Preferably at least 10 mg/kg and more preferably between 50 and 150 mg/kg of sulphur is present in the feed.
A preferred catalyst, which can be used in a non-sulphided form, comprises a non-noble Group VIII metal, e.g., iron, nickel, in conjunction with a Group IB metal, e.g., copper, supported on an acidic support. Copper is preferably present to suppress hydrogenolysis of paraffins to methane. The catalyst has a pore volume preferably in the range of 0.35 to 1.10 ml/g as determined by water absorption, a surface area of preferably between 200-500 m2/g as determined by BET
nitrogen adsorption, and a bulk density of between 0.4-1.0 g/ml. The catalyst support is preferably made of an amorphous silica-alumina wherein the alumina may be present within wide range of between 5 and 96 wt%, preferably between 20 and 85 wto. The silica content as Si02 is preferably between 15 and 80 wt%. Also, the support may contain small amounts, e.g., 20-30 wto, of a binder, e.g., alumina, silica, Group IVA metal oxides, and various types of clays, magnesia, etc., preferably alumina or silica.
The preparation of amorphous silica-alumina microspheres has been described in Ryland, Lloyd B., Tamele, M.W., and Wilson, J.N., Cracking Catalysts, Catalysis: volume VII, Ed. Paul H. Emmett, Reinhold Publishing Corporation, New York, 1960, pp. 5-9.
The catalyst is prepared by co-impregnating the metals from solutions onto the support, drying at 100-150 C, and calcining in air at 200-550 C. The Group VIII metal is present in amounts of about 15 wt% or less, preferably 1-12 wt%, while the Group IB metal is usually present in lesser amounts, e.g., 1:2 to about 1:20 weight ratio respecting the Group VIII metal.
A typical catalyst is shown below:
Ni, wt% 2.5-3.5 Cu, wt% 0.25-0.35 A1203-Si02 wto 65-75 A1203 (binder) wto 25-30 Surface Area 290-325 m2/g Pore Volume (Hg) 0.35-0.45 ml/g Bulk Density 0.58-0.68 g/ml Another class of suitable hydroconversion/
hydroisomerisation catalysts are those based on zeolitic materials, suitably comprising at least one Group VIII
metal component, preferably Pt and/or Pd, as the hydrogenation component. Suitable zeolitic and other aluminosilicate materials, then, include Zeolite beta, Zeolite Y, Ultra Stable Y, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite, mordenite and silica-aluminophosphates, such as SAPO-11 and SAPO-31.
Examples of suitable hydroisomerisation/
hydroisomerisation catalysts are, for instance, described in WO-A-9201657. Combinations of these catalysts are also possible. Very suitable hydroconversion/
hydroisomerisation processes are those involving a first step wherein a zeolite beta or ZSM-48 based catalyst is used and a second step wherein a ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite, mordenite based catalyst is used. Of the latter group ZSM-23, ZSM-22 and ZSM-48 are preferred. Examples of such processes are described in US-A-20040065581, which disclose a process comprising a first step catalyst comprising platinum and zeolite beta and a second step catalyst comprising platinum and ZSM-48.
Combinations wherein the Fischer-Tropsch product is first subjected to a first hydroisomerisation step using the amorphous catalyst comprising a silica-alumina carrier as described above followed by a second hydroisomerisation step using the catalyst comprising the molecular sieve has also been identified as a preferred process to prepare the base oil to be used in the present invention. More preferred the first and second hydroisomerisation steps are performed in series flow.
Most preferred these two steps are performed in a single reactor comprising beds of the above amorphous and/or crystalline catalysts.
In step (a) the feed is contacted with hydrogen in the presence of the catalyst at elevated temperature and pressure. The temperatures typically will be in the range of from 175 to 380 C, preferably higher than 250 C and more preferably from 300 to 370 C. The pressure will typically be in the range of from 10 to 250 bar and preferably between 20 and 80 bar. Hydrogen may be supplied at a gas hourly space velocity of from 100 to 10000 Nl/1/hr, preferably from 500 to 5000 N1/1/hr. The hydrocarbon feed may be provided at a weight hourly space velocity of from 0.1 to 5 kg/1/hr, preferably higher than 0.5 kg/1/hr and more preferably lower than 2 kg/1/hr. The ratio of hydrogen to hydrocarbon feed may range from 100 to 5000 Nl/kg and is preferably from 250 to 2500 N1/kg.
The conversion in step (a) as defined as the weight percentage of the feed boiling above 370 C which reacts per pass to a fraction boiling below 370 C, is at least 20 wt%, preferably at least 25 wt%, but preferably not more than 80 wt%, more preferably not more than 65 wt%.
The feed as used above in the definition is the total hydrocarbon feed fed to step (a), thus also any optional recycle of a high boiling fraction which may be obtained in step (b).
In step (b) the product of step (a) is preferably separated into one or more distillate fuels fractions and a base oil or base oil precursor fraction having the desired viscosity properties. If the pour point is not in the desired range the pour point of the base oil is further reduced by means of a dewaxing step (c), preferably by catalytic dewaxing. In such an embodiment it may be a further advantage to dewax a wider boiling fraction of the product of step (a). From the resulting dewaxed product the base oil and oils having a desired viscosity can then be advantageously isolated by means of distillation. Dewaxing is preferably performed by catalytic dewaxing as for example described in WO-A-02070629, which publication is hereby incorporated by reference. The final boiling point of the feed to the dewaxing step (c) may be the final boiling point of the product of step (a) or lower if desired.
The oil formulation may comprise a single type of base oil or blends of the above-described base oils as base oil composition. Preferably, the present invention further relates to formulations wherein the base oil composition comprises at least 80% by weight of the total formulation of a mineral-derived naphthenic base oil; to formulations wherein the base oil comprises at least 80%
by weight of a mineral-derived paraffinic base oil; and 5 to formulations wherein the base oil composition comprises at least 80% by weight of a Fischer-Tropsch derived base oil.
Also further base oils and other synthetic base oil components may be present in the oil formulation, such as 10 for example esters, poly alpha olefins, as preferably obtained by oligomerisation of an olefinic compound, poly alkylene glycols and the like. Possible base oil compositions preferably include mineral-derived paraffinic base oils and Fischer-Tropsch derived base 15 oils, mineral-derived naphthenic base oils and Fischer-Tropsch derived base oils, and mixtures of the three base oil components.
However, it has been found especially advantageous to use a Fischer-Tropsch derived base oil as the 20 substantially the sole base oil component. With substantially is here meant that more than 80 wt%, more preferably more than 90 wt% and most preferably 100 wt%
of the base oil component in the oil formulation is a Fischer-Tropsch derived base oil as described in detail above.
Additional additives next to the ones described above may also be present in the formulation. The type of additives will depend on the specific application.
Without intending to be limiting, examples of possible additives are dispersants, detergents, viscosity modifying polymers, hydrocarbon or oxygenated hydrocarbon type pour point depressants, emulsifiers, demulsifiers, antistaining additives and friction modifiers. Specific examples of such additives are described in for example Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pages 477-526. Suitably the dispersant is an ashless dispersant, for example polybutylene succinimide polyamines or Mannic base type dispersants. Suitably the detergent is an over-based metallic detergent, for example the phosphonate, sulfonate, phenolate or salicylate types as described in the above referred to General Textbook. Suitably the viscosity modifier is a viscosity modifying polymer, for example polyisobutylenes, olefin copolymers, poly-methacrylates and polyalkylstyrenes and hydrogenated polyisoprene star polymer (Shellvis). Examples of suitable antifoaming agents are polydimethylsiloxanes and polyethylene glycol ethers and esters.
The oil formulation may find use as turbine oil, gasoline engine oil, diesel engine oil, automotive and industrial gear oils, for example automatic and manual transmission and differential oils, hydraulic machine oil, refrigerator oil, plastic processing oil for rolling, press, forging, sqeezing, draw, punch and the like operations, thermal treating oil, discharge processing oil, slide guide oil, rust proofing oil and heat medium. A preferred use of the oil formulation is as electrical oil. It has further been found that when the base oil component of the oil formulation comprises substantially of the Fischer-Tropsch derived base oil an electrical oil formulation is obtained which has good oxidative stability, as expressed by low acid formation and/or low sludge formation and also excellent low temperature viscosity values. Examples of applications are switch gears, transformers, regulators, circuit breakers, power plant reactors, cables and other electrical equipment. A problem often encountered when using an electrical oil based on a naphthenic base oil is that the kinematic viscosity at -30 C is too high. When such an oil would be used in application which have to start up at low temperatures, especially at temperatures below 0 C, the higher viscosity will have a negative effect on the required heat dissipation of the electrical oil. Overheating of the equipment can result. Applicants have found that when a Fischer-Tropsch base oil having a kinematic viscosity at 40 C of between 1 and 15 mm2/sec and a pour point of below -30 C, more preferably below -40 C an electrical oil can be obtained having the above desired properties.
In order to improve the gassing tendency of the oil formulation it is preferred to add between 0.05 and 10 wt%, preferably between 0.1 and 5 wt% of an aromatic compound. Preferred aromatic compounds are for example tertrahydronaphthalene, diethylbenzene, di-isopropylbenzene, a mixture of alkylbenzenes as commercially obtainable as "Shell Oil 4697" or "Shellsol A 150" both "Shell" products obtainable from Shell Deutschland GmbH. Another preferred mixture of aromatic compounds is comprised in a mixture of 2,6-di-t-butyl phenol and 2,6-di-t-butyl cresol. Preferably the oil formulation comprises between 0.1 and 3 wto of 2,6-di-t-butyl phenol and 0.1 to 2 wt% of 2,6-di-t-butyl cresol in a weight ratio of between 1:1 and 1:1.5.
The oil formulation, preferably comprising the anti-wear additive, is preferably subjected to an additional clay treatment. Clay treatment is a well know treatment to remove polar compounds from the oil formulation. It is performed in order to further improve the color, chemical and thermal stability of the oil formulation. It may be performed prior to adding the additives mentioned in this description on a, partly, formulated oil formulation.
Clay treatment processes are for example described in Lubricant base oil and wax processing, Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 229-232. Preferably the copper passivator and optional anti-oxidant are added after the clay treatment.
The oil formulations comprising a Fischer-Tropsch derived base oil as described above show a very low dielectric dissipation factor, even after prolonged testing at elevated temperature. The low dissipation factor is indicative for a low loss of electric power in the application wherein the electrical oil is used.
Because the dissipation factor does not significantly increase over time, especially when compared to the naphthenic based electrical oil formulations, a very efficient application of the oil results.
The electrical oil as described above may find use in applications which have to start up regularly, especially more than 10 times per year at a temperature of below 0 C, more preferably below -5 C, wherein the temperature of the oil when the application is running is above 0 C. Examples of such applications are as low temperature switch gear oils, transformers, regulators, circuit breakers, power plant reactors, switch gear, cables, electrical equipment. Such applications are well known to the skilled person and described for example in Lubricants and related products, Dieter Klamann, Verlag Chemie GmbH, Weinhem, 1984, pages 330-339.
The invention will be illustrated with the following non-limiting examples. In the examples use has been made of four different types of base oils. One Fischer-Tropsch derived base oil, referred to as GTL BO, two naphthenic type of base oils, referred to as naphthenic-1 and naphthenic-2, and a mineral paraffinic base oil. The properties of these base oils are listed in Table 1.
U
.rq 4-I N M ~ M OD N
44 i [- M
~4 U
-H
rl 4-1 H N 0 co U1 l0 r-I
1 CO O ir-I W
r-I
N
rd a U
H ao o d LIl V
J-~ N l-.t;
fL
co z U
-ri 0) rl oD O O l-V l0 d~ d~
J-i N 00 z 0 ao 0o d~ w w ~4 *
N r p a h H I N ri H G+
N
0 O 1I1 O oD
r'1 tn N
r-I N
m H
~
~
~
pUq ~ N u ~i N
r N r ~-+ ~ ~ b) a -a H F1+
~
U) U) tr) ~ ~ w X
U U
E E o 0 E
N Ln 0 0 r- ui N 0 r=
N M dl ~
Q A Q Q Q I~
M
O
J1 ~ 0 o Ll 1:: =-I m N 4-) ri O 0 -ri 0 S-: ~j :J
rl H 0 O 0 W -H t3' A
0 a ~ u ,~ wHG o n o] M
t~ 0 rd S-i ~ U ~
H W x x H a Cz a Q 1~ U 'L3 PU
r-i un ai N
O
tn x: -a U !-I
N
Lfl U
~ Lc4 4J
o \
p a Q N
N
rl N
O Lf) O O ~i 04 H O
U
b r-i U
U =rl =ri ~', Ga N
~ G ~
p ID, G
~4 0 bi U) q a) =r-1 'd ~+
=
d -i U
r-I 4-1 4) N N
=,~ S."
G4 1-) Ul '0 ~r O (.i=' O
a) E
~+ U) 0 q U
U1 =rl t~ 4-I U
N 4-1 =rl ~ ?4 N
(0 CL
r-i 4 r-i 104 o ~ 0 4 ~ ('~., O l0 r= -1 o a 0 0 rn v .~
C rd 1+
0 r.
S~ flS M
t 0 N
U N =~
oW \o N N d' 1) II
tD M
rn o rn 0 u) Ln u1 -ri i.1 ,..i n q, N
x A N ~ 0 Ei OH 4-) Cl ~
-H ~+ 0 ro U
td ~+ C: N 11 U
1~ ~ ~ A N C
bn ~+ b) ~ ?4 rt =~ ,~
~ R4 0 =~ 0 '~ U 0I ~
~ u~~i u aC~q N ~ * 3 ~
Example 1 In Example 1 two formulations A and B were prepared of which the base oil component consisted of 95 wto of the naphthenic-2 base oil and for 5 wt% of the paraffinic-1 base oil. To these mixtures 10 mg/kg of 1-[bis(2-ethylhexyl)aminomethyl]benzotriazole (Reomet38S) was added. To mixture A 200 mg/kg of Dibenzyldisulfide was added and to mixture B 200 mg/kg of Di-n-dodecyldisulfid was added. Oil mixtures A and B were tested with the IEC 61125 C Oxidation test 164h/120 C
test to measure the acidity of the oil phase. The acidity of the oil phase of mixture A was 0.26 mg KOH/g and the acidity of the oil phase of mixture B was 0.94 mg KOH/g.
Both values are very low and illustrate an excellent oxidative stability. The values for Mixture A show that even more excellent results are obtained when the preferred Dibenzyldisulfide additive is used as the an organic polysulphide anti-wear additive. It is surprising that the choice of a particular anti-wear additive can improve the oxidation stability in the manner here illustrated.
Example 2 Starting with the mineral-derived naphthenic-1, mineral-derived paraffin base oil and the GTL base oil-1 of Table 1 five different oil mixtures according to the additivation schemes 1-5 of table 2 were made. For all of these oil mixtures the Sludge Formation was measured according to the Oxidation Test IEC 61125 C at 164h/120 C. The lower the value the less sludge is found.
The results are also presented in Table 2.
From Table 2 it can be seen that the combination of the organic polysulphide anti-wear additive and the copper passivator result in a remarkable low sludge formation. Especially for the mineral paraffin base oils and the Fischer-Tropsch derived base oil the presence of an anti-oxidant further reduces the sludge formation significantly.
m Ln 0 1 Lfl O ~ O N ~ O
N O O~ O O~
r-I l0 r-I
O O o0 00 l-O N O O
N ~
O O O
rI al frl O l0 O cr f7 O 1 l.fl N O
N
O O O
O O M
(Y) [M N
N I ~ I L(1 z:v O
r-i N O
O O lll O dq 0o rl I ~ ~ l- f'') 0 r-i M 0 U bi bi F~
o\0 Ul U~ C/~
N
rI
H
l4 W
M
W N
H E
a rn ~ ~
-~ 0 N
0 ~ (d ~
U -ri ~
U N r-i ~-I r-I r-i (d E N 5C 0 0 0 0 U ~ cl r~ E-+ a) N
-rl Ul 4-I rl 4) x Ul U1 H
~ ~ .a ~ I
~ -~ -~ a) U U 0 4-I fd ~ N 4-1 L: L; N
N 'J >, " 4) -rl a) -rl En -r-I (L) Q r' -ri .1a (d ~
'O Q -r-I 4-3 04 ~-I ~
H v~i ~ Q I rE d ~ a c~.7 For all of these oil mixtures according to additivation schemes 1-5 of above also the Total Acidity using the Oxidation Test IEC 61125 C at 164h/120 C was measured. The lower the value the less acid compounds are 5 formed and the more oxidative stable the oil formulation is. The results are presented in Table 3.
Ln O O O O O r-I
N , . . . .
O r-I O O
("1 00 c-%4' O O m Ln rI
N o c~ ~
rn 00 Ln m O I Ln r- ~
N ~
U r m Ln N ~ O i 00 L~ Ln rI Lfl p N M lfl H
rI
Ln w d~ rn ~
H O ~1 ~1 bl " x x x x x x C\0 H ~
~ i U
U
H
U (1) ro U =
rA
U
=ri -O ~ rl rl Q) 0 ~ r-i ~
~ N ~ H 0 0 O
4-I U ro .c: E=+ a) (1) Ul 4-I H x U2 Ul H
>4 r-i >1 a) x ~a ~ I
A-) r, J g, r-i ~ .Q r-i -H 0 m 41 0 -u -~
'O -r1 -rl Q) N (y U U O
=H 4J 'O I (fS (d =ri =rl U rd r-I N =ri 'o ~ 4) N1 (~ ~> >i ~-1 =r-I ~ =r-I U~
-rl N Ul .0 x 4-I (t a) r+ ~ Fz: -li 0 0 44 W
r-I fd -rl (1) A N -rI (d IQ J-! 'o ~Q F-' -0 Q4 ~-I ~
(d 0 '0 -H 0 rd rtf H
H H (a r-+ ~Q a4 10 Example 3 4 oil mixtures were prepared according to the scheme as presented in Table 4. Two oil mixtures were subjected to a clay treatment using Tonsil 411 clay as obtainable from Sued Chemie, Muenchen (D). The anti-oxidant and copper passivator additives were added after the clay treatment. The properties of the oil mixtures were measured and the oil mixtures were subjected to the IEC
OXIDATION TEST at 500h/120 C.
co O N O C) w O O O M Ln ~ ~{ N
~
ri N
m I-fl O N
Go N
N O O H O M N lfl U) l0 Op I M N ~ O
rl m O p I
O
OD
N O Ln O O r- N
O i ~ m H .
~ C) 0 H V rl ~
o co NI, o rI v M N
M ~ O
O M
~ c~ O H >
Ol O
H 0) O
~D O O M r~
~ H ~ O O
r-I
O Lf1 r-i M N N N I I
01 l0 l0 l0 O 0 ri 0 m in m [~ U1 r I rl H
M M
N H Lf1 lll L(1 O O
0 H H H H w A
H A A A A
m ul EQ
0\0 0\0 0\0 0\0 \ o\0 N r+ c+
11 3 41 41 o\o tl 1.1 U E e ~
i U
~-I o 01%
}4 (0.' ~ ~ 0 O ~ -~ ~
a) -.-i 5 [J4 co E5 (d -~ (a r-i z 0 U1 =H U U 0 =ri r, r-i 0 0 U o H
+-) U 0 ?, o E-~
H ?C N O O W aC
M O O L') 04 ~1 rI ~I .~ E~ J-1 i d~ H F:4 H
44 ri ~ H ~ i ~ H N ~ w ?+ ~+ >4 a ~n + 1 r-i rl m ::5 a) .C r-i 0 E- P H O H
F: -rl ~ ~-I Ul ~ 4J 0 4J E-4 H H H > A
a) 0 U rd =li 41 N N r4 m z p U) m vi P., rLf rd I rd m U) H z O O O
H N i r-i N N -r-1 Z3 =r-I 0 H U U U fY
lw cn a~ ~~~ ~4 -~ 4-) a 0 U) U) u) 0 H
4) (d .(I fd N 1-) t0 J-) ,k', -I W H H H A U
a) r-A Q ~ ~4 r_: =11 0 0 a) x > > >
.El a) a) >1 A N =r-i 04 U) 04 = ~ a a P, F-I A (d 0 1 ~D Z Z Z w w (d (d E-1 (15 =rl -H r-i ~ 41 S I 0 H H H Q$ H
E-~ U) 10 A U -i ,.q a w a x x x a1 A
Ul O
O r-i 04 0 O O' l0 M
Ul N 0 0 N U1 O O O Ln (d 1 V V
N N
O O
J+ N H H
O O O
~ lfl L(1 O 0 rl O
0 V O =
v 0 rI
~ =~ k f~ -k w v r-I
~D
W
U U U
M \ \ \
Ln U) Ln Ln M N N N
H H H
M rl r-i r~
Lfl lO 0 l0 z U U U
H W W W
Q H H H
o\0 rn U v o J..1 0 ~ LI-4 N Ul fd U r-I N G'.
o U 0 O 0 =r-1 r-1 0 0 01 fd IIl 0 ~-I
U O ~ H [~+ 0 =~
-O 0 0 ~ 4-I O 04 U ~I
4-) r-I E-i (d 0 -H U) ;:$
~~ ~C H r-I N Q ~n ~~
~ p 0 ~ 4-4 = 41 ~4 -~
0 r, U r~ (d ~4 U t7~ d ~H Cll N rl bl a) O ~ U) ~ 4) x rl JW ~ U) r-I '14 r I Q~ P4' 0 ~ E-~ JJ U] ~
,~ ~ p; U U U1 O -~ -k ~ rd 0 O x ~
E-i C12 ~4 H H J-1 Lf) Table 4 shows that the oil formulation based on the Fischer-Tropsch derived base oil has a low viscosity at -30 C in combination with excellent oxidative stability properties. The gassing tendency of the Mixture Z of 5 Table 4 can be improved by adding an aromatic solvent as illustrated in Table 5.
Table 5 Sample Identification Z Z' GTL base oil-1 Wto 94,68 94,18 naphthenic base oil-1 Wt%
Mineral Paraffinic base Wt% 5,00 5,00 oil-1 Dibenzyldisulfid (Antiwear Wt% 0,02 0,02 additive) Clay treatment (Tonsil) Wt% 1 1 1-[bis(2-ethylhexyl)amino-Mg/kg 10 10 methyl]benzotriazole Shellsol A 150 (aromatic Wt% none 0,5 hydrocarbon solvent) Antioxidant BHT Wt s 0,30 0,30 GASSING TENDENCY measured according to BS 5797 mm3/min > 0 -8,9 Example 4 Three oil formulations A-C were made using the GTL
Base Oils 1, 2 and 3 of Table 1 according to the 10 formulation as listed in Table 6. The oil formulations A-C were subjected to a clay treatment using Tonsil 411 clay as obtainable from Sued Chemie, Munchen (D).The anti-oxidant and copper passivator additive were added after the clay treatment.
The oils were tested with the test methods listed in Table 6. The results show that excellent oils for use as electrical oils.
Table 6 Oil properties Oil A Oil B Oil C
Formulation GTL BO-1 Wt% 94,7 GTL BO-2 Wt% 98,7 GTL BO-3 Wto 98,7 Paraffinic-base oil 1 Wt% 5,0 Paraffinic-base oil 2 wto 1,0 1,0 Dibenzyldisulfide mg/kg 200 200 200 1- [bis (2-ethylhexyl) -aminomethyl]benzo- mg/kg 10 10 10 triazole Ionol 861805 % 0,3 0,3 0,3 Test results TEST DIMENS.METHODE
DIN ISO
Not DIN measure KIN.VISCOSITY 40 C mm2/s 51562 7,8 17,5 d DIN
KIN.VISCOSITY 100 C mm2/s 51562 2,4 4,1 7,8 IEC OXIDATION TEST 500h/120 C
- Total acidity mgKOH/g 0,02 0,02 0,04 - Sludge Gew.o < 0,006 <0,008 < 0,007 - Dielectr. Dissip. F.
90 C 0,0035 0,0004 0,0004
Combinations wherein the Fischer-Tropsch product is first subjected to a first hydroisomerisation step using the amorphous catalyst comprising a silica-alumina carrier as described above followed by a second hydroisomerisation step using the catalyst comprising the molecular sieve has also been identified as a preferred process to prepare the base oil to be used in the present invention. More preferred the first and second hydroisomerisation steps are performed in series flow.
Most preferred these two steps are performed in a single reactor comprising beds of the above amorphous and/or crystalline catalysts.
In step (a) the feed is contacted with hydrogen in the presence of the catalyst at elevated temperature and pressure. The temperatures typically will be in the range of from 175 to 380 C, preferably higher than 250 C and more preferably from 300 to 370 C. The pressure will typically be in the range of from 10 to 250 bar and preferably between 20 and 80 bar. Hydrogen may be supplied at a gas hourly space velocity of from 100 to 10000 Nl/1/hr, preferably from 500 to 5000 N1/1/hr. The hydrocarbon feed may be provided at a weight hourly space velocity of from 0.1 to 5 kg/1/hr, preferably higher than 0.5 kg/1/hr and more preferably lower than 2 kg/1/hr. The ratio of hydrogen to hydrocarbon feed may range from 100 to 5000 Nl/kg and is preferably from 250 to 2500 N1/kg.
The conversion in step (a) as defined as the weight percentage of the feed boiling above 370 C which reacts per pass to a fraction boiling below 370 C, is at least 20 wt%, preferably at least 25 wt%, but preferably not more than 80 wt%, more preferably not more than 65 wt%.
The feed as used above in the definition is the total hydrocarbon feed fed to step (a), thus also any optional recycle of a high boiling fraction which may be obtained in step (b).
In step (b) the product of step (a) is preferably separated into one or more distillate fuels fractions and a base oil or base oil precursor fraction having the desired viscosity properties. If the pour point is not in the desired range the pour point of the base oil is further reduced by means of a dewaxing step (c), preferably by catalytic dewaxing. In such an embodiment it may be a further advantage to dewax a wider boiling fraction of the product of step (a). From the resulting dewaxed product the base oil and oils having a desired viscosity can then be advantageously isolated by means of distillation. Dewaxing is preferably performed by catalytic dewaxing as for example described in WO-A-02070629, which publication is hereby incorporated by reference. The final boiling point of the feed to the dewaxing step (c) may be the final boiling point of the product of step (a) or lower if desired.
The oil formulation may comprise a single type of base oil or blends of the above-described base oils as base oil composition. Preferably, the present invention further relates to formulations wherein the base oil composition comprises at least 80% by weight of the total formulation of a mineral-derived naphthenic base oil; to formulations wherein the base oil comprises at least 80%
by weight of a mineral-derived paraffinic base oil; and 5 to formulations wherein the base oil composition comprises at least 80% by weight of a Fischer-Tropsch derived base oil.
Also further base oils and other synthetic base oil components may be present in the oil formulation, such as 10 for example esters, poly alpha olefins, as preferably obtained by oligomerisation of an olefinic compound, poly alkylene glycols and the like. Possible base oil compositions preferably include mineral-derived paraffinic base oils and Fischer-Tropsch derived base 15 oils, mineral-derived naphthenic base oils and Fischer-Tropsch derived base oils, and mixtures of the three base oil components.
However, it has been found especially advantageous to use a Fischer-Tropsch derived base oil as the 20 substantially the sole base oil component. With substantially is here meant that more than 80 wt%, more preferably more than 90 wt% and most preferably 100 wt%
of the base oil component in the oil formulation is a Fischer-Tropsch derived base oil as described in detail above.
Additional additives next to the ones described above may also be present in the formulation. The type of additives will depend on the specific application.
Without intending to be limiting, examples of possible additives are dispersants, detergents, viscosity modifying polymers, hydrocarbon or oxygenated hydrocarbon type pour point depressants, emulsifiers, demulsifiers, antistaining additives and friction modifiers. Specific examples of such additives are described in for example Kirk-Othmer Encyclopedia of Chemical Technology, third edition, volume 14, pages 477-526. Suitably the dispersant is an ashless dispersant, for example polybutylene succinimide polyamines or Mannic base type dispersants. Suitably the detergent is an over-based metallic detergent, for example the phosphonate, sulfonate, phenolate or salicylate types as described in the above referred to General Textbook. Suitably the viscosity modifier is a viscosity modifying polymer, for example polyisobutylenes, olefin copolymers, poly-methacrylates and polyalkylstyrenes and hydrogenated polyisoprene star polymer (Shellvis). Examples of suitable antifoaming agents are polydimethylsiloxanes and polyethylene glycol ethers and esters.
The oil formulation may find use as turbine oil, gasoline engine oil, diesel engine oil, automotive and industrial gear oils, for example automatic and manual transmission and differential oils, hydraulic machine oil, refrigerator oil, plastic processing oil for rolling, press, forging, sqeezing, draw, punch and the like operations, thermal treating oil, discharge processing oil, slide guide oil, rust proofing oil and heat medium. A preferred use of the oil formulation is as electrical oil. It has further been found that when the base oil component of the oil formulation comprises substantially of the Fischer-Tropsch derived base oil an electrical oil formulation is obtained which has good oxidative stability, as expressed by low acid formation and/or low sludge formation and also excellent low temperature viscosity values. Examples of applications are switch gears, transformers, regulators, circuit breakers, power plant reactors, cables and other electrical equipment. A problem often encountered when using an electrical oil based on a naphthenic base oil is that the kinematic viscosity at -30 C is too high. When such an oil would be used in application which have to start up at low temperatures, especially at temperatures below 0 C, the higher viscosity will have a negative effect on the required heat dissipation of the electrical oil. Overheating of the equipment can result. Applicants have found that when a Fischer-Tropsch base oil having a kinematic viscosity at 40 C of between 1 and 15 mm2/sec and a pour point of below -30 C, more preferably below -40 C an electrical oil can be obtained having the above desired properties.
In order to improve the gassing tendency of the oil formulation it is preferred to add between 0.05 and 10 wt%, preferably between 0.1 and 5 wt% of an aromatic compound. Preferred aromatic compounds are for example tertrahydronaphthalene, diethylbenzene, di-isopropylbenzene, a mixture of alkylbenzenes as commercially obtainable as "Shell Oil 4697" or "Shellsol A 150" both "Shell" products obtainable from Shell Deutschland GmbH. Another preferred mixture of aromatic compounds is comprised in a mixture of 2,6-di-t-butyl phenol and 2,6-di-t-butyl cresol. Preferably the oil formulation comprises between 0.1 and 3 wto of 2,6-di-t-butyl phenol and 0.1 to 2 wt% of 2,6-di-t-butyl cresol in a weight ratio of between 1:1 and 1:1.5.
The oil formulation, preferably comprising the anti-wear additive, is preferably subjected to an additional clay treatment. Clay treatment is a well know treatment to remove polar compounds from the oil formulation. It is performed in order to further improve the color, chemical and thermal stability of the oil formulation. It may be performed prior to adding the additives mentioned in this description on a, partly, formulated oil formulation.
Clay treatment processes are for example described in Lubricant base oil and wax processing, Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4, pages 229-232. Preferably the copper passivator and optional anti-oxidant are added after the clay treatment.
The oil formulations comprising a Fischer-Tropsch derived base oil as described above show a very low dielectric dissipation factor, even after prolonged testing at elevated temperature. The low dissipation factor is indicative for a low loss of electric power in the application wherein the electrical oil is used.
Because the dissipation factor does not significantly increase over time, especially when compared to the naphthenic based electrical oil formulations, a very efficient application of the oil results.
The electrical oil as described above may find use in applications which have to start up regularly, especially more than 10 times per year at a temperature of below 0 C, more preferably below -5 C, wherein the temperature of the oil when the application is running is above 0 C. Examples of such applications are as low temperature switch gear oils, transformers, regulators, circuit breakers, power plant reactors, switch gear, cables, electrical equipment. Such applications are well known to the skilled person and described for example in Lubricants and related products, Dieter Klamann, Verlag Chemie GmbH, Weinhem, 1984, pages 330-339.
The invention will be illustrated with the following non-limiting examples. In the examples use has been made of four different types of base oils. One Fischer-Tropsch derived base oil, referred to as GTL BO, two naphthenic type of base oils, referred to as naphthenic-1 and naphthenic-2, and a mineral paraffinic base oil. The properties of these base oils are listed in Table 1.
U
.rq 4-I N M ~ M OD N
44 i [- M
~4 U
-H
rl 4-1 H N 0 co U1 l0 r-I
1 CO O ir-I W
r-I
N
rd a U
H ao o d LIl V
J-~ N l-.t;
fL
co z U
-ri 0) rl oD O O l-V l0 d~ d~
J-i N 00 z 0 ao 0o d~ w w ~4 *
N r p a h H I N ri H G+
N
0 O 1I1 O oD
r'1 tn N
r-I N
m H
~
~
~
pUq ~ N u ~i N
r N r ~-+ ~ ~ b) a -a H F1+
~
U) U) tr) ~ ~ w X
U U
E E o 0 E
N Ln 0 0 r- ui N 0 r=
N M dl ~
Q A Q Q Q I~
M
O
J1 ~ 0 o Ll 1:: =-I m N 4-) ri O 0 -ri 0 S-: ~j :J
rl H 0 O 0 W -H t3' A
0 a ~ u ,~ wHG o n o] M
t~ 0 rd S-i ~ U ~
H W x x H a Cz a Q 1~ U 'L3 PU
r-i un ai N
O
tn x: -a U !-I
N
Lfl U
~ Lc4 4J
o \
p a Q N
N
rl N
O Lf) O O ~i 04 H O
U
b r-i U
U =rl =ri ~', Ga N
~ G ~
p ID, G
~4 0 bi U) q a) =r-1 'd ~+
=
d -i U
r-I 4-1 4) N N
=,~ S."
G4 1-) Ul '0 ~r O (.i=' O
a) E
~+ U) 0 q U
U1 =rl t~ 4-I U
N 4-1 =rl ~ ?4 N
(0 CL
r-i 4 r-i 104 o ~ 0 4 ~ ('~., O l0 r= -1 o a 0 0 rn v .~
C rd 1+
0 r.
S~ flS M
t 0 N
U N =~
oW \o N N d' 1) II
tD M
rn o rn 0 u) Ln u1 -ri i.1 ,..i n q, N
x A N ~ 0 Ei OH 4-) Cl ~
-H ~+ 0 ro U
td ~+ C: N 11 U
1~ ~ ~ A N C
bn ~+ b) ~ ?4 rt =~ ,~
~ R4 0 =~ 0 '~ U 0I ~
~ u~~i u aC~q N ~ * 3 ~
Example 1 In Example 1 two formulations A and B were prepared of which the base oil component consisted of 95 wto of the naphthenic-2 base oil and for 5 wt% of the paraffinic-1 base oil. To these mixtures 10 mg/kg of 1-[bis(2-ethylhexyl)aminomethyl]benzotriazole (Reomet38S) was added. To mixture A 200 mg/kg of Dibenzyldisulfide was added and to mixture B 200 mg/kg of Di-n-dodecyldisulfid was added. Oil mixtures A and B were tested with the IEC 61125 C Oxidation test 164h/120 C
test to measure the acidity of the oil phase. The acidity of the oil phase of mixture A was 0.26 mg KOH/g and the acidity of the oil phase of mixture B was 0.94 mg KOH/g.
Both values are very low and illustrate an excellent oxidative stability. The values for Mixture A show that even more excellent results are obtained when the preferred Dibenzyldisulfide additive is used as the an organic polysulphide anti-wear additive. It is surprising that the choice of a particular anti-wear additive can improve the oxidation stability in the manner here illustrated.
Example 2 Starting with the mineral-derived naphthenic-1, mineral-derived paraffin base oil and the GTL base oil-1 of Table 1 five different oil mixtures according to the additivation schemes 1-5 of table 2 were made. For all of these oil mixtures the Sludge Formation was measured according to the Oxidation Test IEC 61125 C at 164h/120 C. The lower the value the less sludge is found.
The results are also presented in Table 2.
From Table 2 it can be seen that the combination of the organic polysulphide anti-wear additive and the copper passivator result in a remarkable low sludge formation. Especially for the mineral paraffin base oils and the Fischer-Tropsch derived base oil the presence of an anti-oxidant further reduces the sludge formation significantly.
m Ln 0 1 Lfl O ~ O N ~ O
N O O~ O O~
r-I l0 r-I
O O o0 00 l-O N O O
N ~
O O O
rI al frl O l0 O cr f7 O 1 l.fl N O
N
O O O
O O M
(Y) [M N
N I ~ I L(1 z:v O
r-i N O
O O lll O dq 0o rl I ~ ~ l- f'') 0 r-i M 0 U bi bi F~
o\0 Ul U~ C/~
N
rI
H
l4 W
M
W N
H E
a rn ~ ~
-~ 0 N
0 ~ (d ~
U -ri ~
U N r-i ~-I r-I r-i (d E N 5C 0 0 0 0 U ~ cl r~ E-+ a) N
-rl Ul 4-I rl 4) x Ul U1 H
~ ~ .a ~ I
~ -~ -~ a) U U 0 4-I fd ~ N 4-1 L: L; N
N 'J >, " 4) -rl a) -rl En -r-I (L) Q r' -ri .1a (d ~
'O Q -r-I 4-3 04 ~-I ~
H v~i ~ Q I rE d ~ a c~.7 For all of these oil mixtures according to additivation schemes 1-5 of above also the Total Acidity using the Oxidation Test IEC 61125 C at 164h/120 C was measured. The lower the value the less acid compounds are 5 formed and the more oxidative stable the oil formulation is. The results are presented in Table 3.
Ln O O O O O r-I
N , . . . .
O r-I O O
("1 00 c-%4' O O m Ln rI
N o c~ ~
rn 00 Ln m O I Ln r- ~
N ~
U r m Ln N ~ O i 00 L~ Ln rI Lfl p N M lfl H
rI
Ln w d~ rn ~
H O ~1 ~1 bl " x x x x x x C\0 H ~
~ i U
U
H
U (1) ro U =
rA
U
=ri -O ~ rl rl Q) 0 ~ r-i ~
~ N ~ H 0 0 O
4-I U ro .c: E=+ a) (1) Ul 4-I H x U2 Ul H
>4 r-i >1 a) x ~a ~ I
A-) r, J g, r-i ~ .Q r-i -H 0 m 41 0 -u -~
'O -r1 -rl Q) N (y U U O
=H 4J 'O I (fS (d =ri =rl U rd r-I N =ri 'o ~ 4) N1 (~ ~> >i ~-1 =r-I ~ =r-I U~
-rl N Ul .0 x 4-I (t a) r+ ~ Fz: -li 0 0 44 W
r-I fd -rl (1) A N -rI (d IQ J-! 'o ~Q F-' -0 Q4 ~-I ~
(d 0 '0 -H 0 rd rtf H
H H (a r-+ ~Q a4 10 Example 3 4 oil mixtures were prepared according to the scheme as presented in Table 4. Two oil mixtures were subjected to a clay treatment using Tonsil 411 clay as obtainable from Sued Chemie, Muenchen (D). The anti-oxidant and copper passivator additives were added after the clay treatment. The properties of the oil mixtures were measured and the oil mixtures were subjected to the IEC
OXIDATION TEST at 500h/120 C.
co O N O C) w O O O M Ln ~ ~{ N
~
ri N
m I-fl O N
Go N
N O O H O M N lfl U) l0 Op I M N ~ O
rl m O p I
O
OD
N O Ln O O r- N
O i ~ m H .
~ C) 0 H V rl ~
o co NI, o rI v M N
M ~ O
O M
~ c~ O H >
Ol O
H 0) O
~D O O M r~
~ H ~ O O
r-I
O Lf1 r-i M N N N I I
01 l0 l0 l0 O 0 ri 0 m in m [~ U1 r I rl H
M M
N H Lf1 lll L(1 O O
0 H H H H w A
H A A A A
m ul EQ
0\0 0\0 0\0 0\0 \ o\0 N r+ c+
11 3 41 41 o\o tl 1.1 U E e ~
i U
~-I o 01%
}4 (0.' ~ ~ 0 O ~ -~ ~
a) -.-i 5 [J4 co E5 (d -~ (a r-i z 0 U1 =H U U 0 =ri r, r-i 0 0 U o H
+-) U 0 ?, o E-~
H ?C N O O W aC
M O O L') 04 ~1 rI ~I .~ E~ J-1 i d~ H F:4 H
44 ri ~ H ~ i ~ H N ~ w ?+ ~+ >4 a ~n + 1 r-i rl m ::5 a) .C r-i 0 E- P H O H
F: -rl ~ ~-I Ul ~ 4J 0 4J E-4 H H H > A
a) 0 U rd =li 41 N N r4 m z p U) m vi P., rLf rd I rd m U) H z O O O
H N i r-i N N -r-1 Z3 =r-I 0 H U U U fY
lw cn a~ ~~~ ~4 -~ 4-) a 0 U) U) u) 0 H
4) (d .(I fd N 1-) t0 J-) ,k', -I W H H H A U
a) r-A Q ~ ~4 r_: =11 0 0 a) x > > >
.El a) a) >1 A N =r-i 04 U) 04 = ~ a a P, F-I A (d 0 1 ~D Z Z Z w w (d (d E-1 (15 =rl -H r-i ~ 41 S I 0 H H H Q$ H
E-~ U) 10 A U -i ,.q a w a x x x a1 A
Ul O
O r-i 04 0 O O' l0 M
Ul N 0 0 N U1 O O O Ln (d 1 V V
N N
O O
J+ N H H
O O O
~ lfl L(1 O 0 rl O
0 V O =
v 0 rI
~ =~ k f~ -k w v r-I
~D
W
U U U
M \ \ \
Ln U) Ln Ln M N N N
H H H
M rl r-i r~
Lfl lO 0 l0 z U U U
H W W W
Q H H H
o\0 rn U v o J..1 0 ~ LI-4 N Ul fd U r-I N G'.
o U 0 O 0 =r-1 r-1 0 0 01 fd IIl 0 ~-I
U O ~ H [~+ 0 =~
-O 0 0 ~ 4-I O 04 U ~I
4-) r-I E-i (d 0 -H U) ;:$
~~ ~C H r-I N Q ~n ~~
~ p 0 ~ 4-4 = 41 ~4 -~
0 r, U r~ (d ~4 U t7~ d ~H Cll N rl bl a) O ~ U) ~ 4) x rl JW ~ U) r-I '14 r I Q~ P4' 0 ~ E-~ JJ U] ~
,~ ~ p; U U U1 O -~ -k ~ rd 0 O x ~
E-i C12 ~4 H H J-1 Lf) Table 4 shows that the oil formulation based on the Fischer-Tropsch derived base oil has a low viscosity at -30 C in combination with excellent oxidative stability properties. The gassing tendency of the Mixture Z of 5 Table 4 can be improved by adding an aromatic solvent as illustrated in Table 5.
Table 5 Sample Identification Z Z' GTL base oil-1 Wto 94,68 94,18 naphthenic base oil-1 Wt%
Mineral Paraffinic base Wt% 5,00 5,00 oil-1 Dibenzyldisulfid (Antiwear Wt% 0,02 0,02 additive) Clay treatment (Tonsil) Wt% 1 1 1-[bis(2-ethylhexyl)amino-Mg/kg 10 10 methyl]benzotriazole Shellsol A 150 (aromatic Wt% none 0,5 hydrocarbon solvent) Antioxidant BHT Wt s 0,30 0,30 GASSING TENDENCY measured according to BS 5797 mm3/min > 0 -8,9 Example 4 Three oil formulations A-C were made using the GTL
Base Oils 1, 2 and 3 of Table 1 according to the 10 formulation as listed in Table 6. The oil formulations A-C were subjected to a clay treatment using Tonsil 411 clay as obtainable from Sued Chemie, Munchen (D).The anti-oxidant and copper passivator additive were added after the clay treatment.
The oils were tested with the test methods listed in Table 6. The results show that excellent oils for use as electrical oils.
Table 6 Oil properties Oil A Oil B Oil C
Formulation GTL BO-1 Wt% 94,7 GTL BO-2 Wt% 98,7 GTL BO-3 Wto 98,7 Paraffinic-base oil 1 Wt% 5,0 Paraffinic-base oil 2 wto 1,0 1,0 Dibenzyldisulfide mg/kg 200 200 200 1- [bis (2-ethylhexyl) -aminomethyl]benzo- mg/kg 10 10 10 triazole Ionol 861805 % 0,3 0,3 0,3 Test results TEST DIMENS.METHODE
DIN ISO
Not DIN measure KIN.VISCOSITY 40 C mm2/s 51562 7,8 17,5 d DIN
KIN.VISCOSITY 100 C mm2/s 51562 2,4 4,1 7,8 IEC OXIDATION TEST 500h/120 C
- Total acidity mgKOH/g 0,02 0,02 0,04 - Sludge Gew.o < 0,006 <0,008 < 0,007 - Dielectr. Dissip. F.
90 C 0,0035 0,0004 0,0004
Claims (21)
1. Oxidation stable oil formulation comprising a base oil composition comprising a mineral-derived naphthenic base oil, a mineral-derived paraffinic base oil, and/or a Fischer-Tropsch derived paraffinic base oil, a copper passivator and at most 0.1 wt% of an organic sulphur or phosphorus anti-wear additive.
2. Formulation according to claim 1, wherein the anti-wear additive comprises an organic polysulfide represented by the formula R1-(S)a-R2 (I) wherein:
a is 2, 3, 4 or 5;
R1 and R2 are independently selected from the group consisting of optionally substituted, straight or branched, saturated or unsaturated C1-C25 hydrocarbon groups.
a is 2, 3, 4 or 5;
R1 and R2 are independently selected from the group consisting of optionally substituted, straight or branched, saturated or unsaturated C1-C25 hydrocarbon groups.
3. Formulation according to claim 2, wherein R1 and R2 are independently selected from the group consisting of optionally substituted, straight or branched, aromatic or aliphatic C4-C20, preferably C6-C14 hydrocarbon groups.
4. Formulation according to claim 3, wherein R1 and R2 are independently selected from straight or branched dodecyl and benzyl.
5. Formulation according to one or more of the preceding claims, wherein the content of organic sulphur or phosphorus anti-wear additive in the formulation is less than 800 mg/kg, more preferably less than 400 mg/kg.
6. Formulation according to one or more of the preceding claims, wherein the copper passivator is a compound according to formula (II) or an optionally substituted benzotriazole compound represented by the formula (III) wherein R4 may be hydrogen or a group represented by the formula (IV) or by the formula (V) wherein:
c is 0, 1, 2 or 3;
R3 is a straight or branched C1-4 alkyl group; R5 is a methylene or ethylene group; R6 and R7 are hydrogen or the same or different straight or branched alkyl groups of 1-18 carbon atoms, preferably a branched alkyl group of 1-12 carbon atoms; R8 and R9 are the same or different alkyl groups of 3-15 carbon atoms.
c is 0, 1, 2 or 3;
R3 is a straight or branched C1-4 alkyl group; R5 is a methylene or ethylene group; R6 and R7 are hydrogen or the same or different straight or branched alkyl groups of 1-18 carbon atoms, preferably a branched alkyl group of 1-12 carbon atoms; R8 and R9 are the same or different alkyl groups of 3-15 carbon atoms.
7. Formulation according to claim 6, wherein R3 is methyl or ethyl and C is 1 or 2.
8. Formulation according to any one of claims 1-6, wherein the content of the copper passivator additive is between 5 and 1000 mg/kg.
9. Formulation according to any one of claims 1-7, wherein the formulation has a sulphur content of below 0.5 wt%.
10. Formulation according to any one of claims 1-8 also containing an anti-oxidant additive.
11. Formulation according to claim 10, wherein the anti-oxidant additive is a phenolic or amine antioxidant.
12. Formulation according to claim 11, wherein the anti-oxidant additive is ditert.-butylated hydroxotoluene.
13. Formulation according to any one of claims 1-12, wherein the base oil composition comprises at least 80%
by weight of a mineral-derived naphthenic base oil.
by weight of a mineral-derived naphthenic base oil.
14. Formulation according to any one of claims 1-12, wherein the base oil composition comprises at least 80%
by weight of a mineral-derived paraffinic base oil.
by weight of a mineral-derived paraffinic base oil.
15. Formulation according to any one of claim 1-12, wherein the base oil composition comprises at least 80%
by weight of a Fischer-Tropsch derived base oil.
by weight of a Fischer-Tropsch derived base oil.
16. Formulation according to any one of claims 1-15, wherein the kinematic viscosity at 40 °C of the base oil composition is between 1 and 4 mm2/sec.
17. Formulation according to any one of claims 1-15, wherein the kinematic viscosity at 40 °C of the base oil composition is between 5 and 15 mm2/sec.
18. Process to prepare a formulation according to any one of claims 1-17, wherein a mixture of the base oil composition and the organic sulphur or phosphorus anti-wear additive is subjected to a clay treatment and wherein the copper passivator is added after performing the clay treatment.
19. Use of the formulation according to one or more of the preceding claims as an electrical oil.
20. Use of the formulation according to claim 19 as a low temperature switch gear application.
21. Use of the formulation according to claim 19 as a transformer oil.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05013535.9 | 2005-06-23 | ||
EP05013535 | 2005-06-23 | ||
PCT/EP2006/063433 WO2006136591A1 (en) | 2005-06-23 | 2006-06-22 | Oxidative stable oil formulation |
Publications (1)
Publication Number | Publication Date |
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CA2611649A1 true CA2611649A1 (en) | 2006-12-28 |
Family
ID=35220516
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002611649A Abandoned CA2611649A1 (en) | 2005-06-23 | 2006-06-22 | Oxidative stable oil formulation |
Country Status (12)
Country | Link |
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US (1) | US20090082235A1 (en) |
EP (1) | EP1896556B1 (en) |
JP (1) | JP5420241B2 (en) |
KR (1) | KR20080025746A (en) |
CN (1) | CN101198680B (en) |
AU (1) | AU2006260919A1 (en) |
BR (1) | BRPI0611906B1 (en) |
CA (1) | CA2611649A1 (en) |
RU (1) | RU2416628C2 (en) |
TW (1) | TW200728447A (en) |
WO (1) | WO2006136591A1 (en) |
ZA (1) | ZA200709550B (en) |
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- 2006-06-22 TW TW095122447A patent/TW200728447A/en unknown
- 2006-06-22 BR BRPI0611906A patent/BRPI0611906B1/en active IP Right Grant
- 2006-06-22 CA CA002611649A patent/CA2611649A1/en not_active Abandoned
- 2006-06-22 AU AU2006260919A patent/AU2006260919A1/en not_active Abandoned
- 2006-06-22 CN CN2006800211650A patent/CN101198680B/en active Active
- 2006-06-22 EP EP06777414.1A patent/EP1896556B1/en active Active
- 2006-06-22 KR KR1020087001792A patent/KR20080025746A/en not_active Application Discontinuation
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BRPI0611906A2 (en) | 2011-02-22 |
CN101198680B (en) | 2012-03-21 |
ZA200709550B (en) | 2008-11-26 |
EP1896556A1 (en) | 2008-03-12 |
KR20080025746A (en) | 2008-03-21 |
US20090082235A1 (en) | 2009-03-26 |
WO2006136591A1 (en) | 2006-12-28 |
JP5420241B2 (en) | 2014-02-19 |
JP2008544057A (en) | 2008-12-04 |
CN101198680A (en) | 2008-06-11 |
RU2416628C2 (en) | 2011-04-20 |
EP1896556B1 (en) | 2018-09-26 |
RU2008102362A (en) | 2009-07-27 |
AU2006260919A1 (en) | 2006-12-28 |
TW200728447A (en) | 2007-08-01 |
BRPI0611906B1 (en) | 2015-09-08 |
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