JP5166783B2 - Lubricating oil composition for turbine equipment provided with compressor and speed increasing gear device - Google Patents
Lubricating oil composition for turbine equipment provided with compressor and speed increasing gear device Download PDFInfo
- Publication number
- JP5166783B2 JP5166783B2 JP2007163549A JP2007163549A JP5166783B2 JP 5166783 B2 JP5166783 B2 JP 5166783B2 JP 2007163549 A JP2007163549 A JP 2007163549A JP 2007163549 A JP2007163549 A JP 2007163549A JP 5166783 B2 JP5166783 B2 JP 5166783B2
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- JP
- Japan
- Prior art keywords
- lubricating oil
- turbine
- compressor
- oil composition
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000010687 lubricating oil Substances 0.000 title claims description 49
- 239000000203 mixture Substances 0.000 title claims description 47
- 230000001965 increasing effect Effects 0.000 title claims description 19
- -1 phosphorus compound Chemical group 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 239000003921 oil Substances 0.000 claims description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 21
- 239000002199 base oil Substances 0.000 claims description 20
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 10
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 10
- 239000001384 succinic acid Substances 0.000 claims description 10
- 150000002332 glycine derivatives Chemical class 0.000 claims description 9
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010446 mineral oil Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 5
- 230000036961 partial effect Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 description 40
- 239000010452 phosphate Substances 0.000 description 40
- 238000012360 testing method Methods 0.000 description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 34
- 239000002253 acid Substances 0.000 description 32
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 25
- 230000003647 oxidation Effects 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 15
- 239000000654 additive Substances 0.000 description 15
- 230000002265 prevention Effects 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 239000010802 sludge Substances 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 11
- 238000010248 power generation Methods 0.000 description 11
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 239000010723 turbine oil Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 239000012208 gear oil Substances 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- FACIWBZCZQRQBU-UHFFFAOYSA-N dipentadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCC FACIWBZCZQRQBU-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002333 glycines Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- XKMCVHMWMWTINX-UHFFFAOYSA-N (2,3,4-trichlorophenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=C(Cl)C(Cl)=C1Cl XKMCVHMWMWTINX-UHFFFAOYSA-N 0.000 description 1
- OJUZRFGUKHQNJX-UHFFFAOYSA-N (4-methylphenyl) diphenyl phosphate Chemical compound C1=CC(C)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 OJUZRFGUKHQNJX-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 108010064754 1-ene-dehydrogenase Proteins 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- GGQRKYMKYMRZTF-UHFFFAOYSA-N 2,2,3,3-tetrakis(prop-1-enyl)butanedioic acid Chemical compound CC=CC(C=CC)(C(O)=O)C(C=CC)(C=CC)C(O)=O GGQRKYMKYMRZTF-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- NPRQLWMILWHEDI-UHFFFAOYSA-N 3-[bis(2-methylpropoxy)phosphinothioylsulfanyl]-2-methylpropanoic acid Chemical compound CC(C)COP(=S)(OCC(C)C)SCC(C)C(O)=O NPRQLWMILWHEDI-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZZGHZLUTIKGEDL-UHFFFAOYSA-M C(CC(C)C)SP(=S)(OCCC(C)C)[O-].[Zn+] Chemical compound C(CC(C)C)SP(=S)(OCCC(C)C)[O-].[Zn+] ZZGHZLUTIKGEDL-UHFFFAOYSA-M 0.000 description 1
- AOICMAWCVGIYLG-UHFFFAOYSA-N C(CC)C=1C(=C(C=CC1)S(=P([S-])([O-])[O-])C)CCC.[Zn+2].C(CC)C=1C(=C(C=CC1)S(=P([S-])([O-])[O-])C)CCC.[Zn+2].[Zn+2] Chemical compound C(CC)C=1C(=C(C=CC1)S(=P([S-])([O-])[O-])C)CCC.[Zn+2].C(CC)C=1C(=C(C=CC1)S(=P([S-])([O-])[O-])C)CCC.[Zn+2].[Zn+2] AOICMAWCVGIYLG-UHFFFAOYSA-N 0.000 description 1
- ISRPMTWTAKYJJI-UHFFFAOYSA-N CCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCC.CCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCC.[Zn+2].[Zn+2].[Zn+2] Chemical compound CCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCC.CCCC1=CC=CC([S+]=P([O-])([O-])[S-])=C1CCC.[Zn+2].[Zn+2].[Zn+2] ISRPMTWTAKYJJI-UHFFFAOYSA-N 0.000 description 1
- NIGWBUOGUODAAT-UHFFFAOYSA-N CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].[Zn+2].[Zn+2].[Zn+2] Chemical compound CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].CCCCCC(CC)(CC)[S+]=P([O-])([O-])[S-].[Zn+2].[Zn+2].[Zn+2] NIGWBUOGUODAAT-UHFFFAOYSA-N 0.000 description 1
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- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- ZATMWXRIJNLIBA-UHFFFAOYSA-N triheptadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCC ZATMWXRIJNLIBA-UHFFFAOYSA-N 0.000 description 1
- GSURLQOINUQIIH-UHFFFAOYSA-N triheptyl phosphate Chemical compound CCCCCCCOP(=O)(OCCCCCCC)OCCCCCCC GSURLQOINUQIIH-UHFFFAOYSA-N 0.000 description 1
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- QUTZUATVZPXUJR-UHFFFAOYSA-N trinonyl phosphite Chemical compound CCCCCCCCCOP(OCCCCCCCCC)OCCCCCCCCC QUTZUATVZPXUJR-UHFFFAOYSA-N 0.000 description 1
- FDGZUBKNYGBWHI-UHFFFAOYSA-N trioctadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC FDGZUBKNYGBWHI-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- OEOJDBBVRPAIDK-UHFFFAOYSA-N tripentadecyl phosphate Chemical compound CCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCC OEOJDBBVRPAIDK-UHFFFAOYSA-N 0.000 description 1
- KRGWQWQLDWWLIB-UHFFFAOYSA-N tripentoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound CCCCCOP(=S)(OCCCCC)OCCCCC KRGWQWQLDWWLIB-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- CVWUIWZKLYGDNJ-UHFFFAOYSA-N tripentyl phosphite Chemical compound CCCCCOP(OCCCCC)OCCCCC CVWUIWZKLYGDNJ-UHFFFAOYSA-N 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
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- PYFJQRSJTZCTPX-UHFFFAOYSA-N tris(2,3-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(OP(OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C PYFJQRSJTZCTPX-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- XHTMGDWCCPGGET-UHFFFAOYSA-N tris(3,3-dichloropropyl) phosphate Chemical compound ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl XHTMGDWCCPGGET-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- SVETUDAIEHYIKZ-IUPFWZBJSA-N tris[(z)-octadec-9-enyl] phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(=O)(OCCCCCCCC\C=C/CCCCCCCC)OCCCCCCCC\C=C/CCCCCCCC SVETUDAIEHYIKZ-IUPFWZBJSA-N 0.000 description 1
- WYFGCJADJYRNAK-UHFFFAOYSA-N tritetradecyl phosphate Chemical compound CCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCC)OCCCCCCCCCCCCCC WYFGCJADJYRNAK-UHFFFAOYSA-N 0.000 description 1
- XEQUZHYCHCGTJX-UHFFFAOYSA-N tritridecyl phosphate Chemical compound CCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC XEQUZHYCHCGTJX-UHFFFAOYSA-N 0.000 description 1
- SUZOHRHSQCIJDK-UHFFFAOYSA-N triundecyl phosphate Chemical compound CCCCCCCCCCCOP(=O)(OCCCCCCCCCCC)OCCCCCCCCCCC SUZOHRHSQCIJDK-UHFFFAOYSA-N 0.000 description 1
- UKPASDNOVTUNJT-UHFFFAOYSA-N triundecyl phosphite Chemical compound CCCCCCCCCCCOP(OCCCCCCCCCCC)OCCCCCCCCCCC UKPASDNOVTUNJT-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- ZNCAMSISVWKWHL-UHFFFAOYSA-L zinc;butoxy-butylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([O-])(=S)SCCCC.CCCCOP([O-])(=S)SCCCC ZNCAMSISVWKWHL-UHFFFAOYSA-L 0.000 description 1
- ZBDJNBFTEIUHPK-UHFFFAOYSA-L zinc;dihexoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCOP([S-])(=S)OCCCCCC.CCCCCCOP([S-])(=S)OCCCCCC ZBDJNBFTEIUHPK-UHFFFAOYSA-L 0.000 description 1
- AEXHGRVJDVETQU-UHFFFAOYSA-L zinc;nonylsulfanyl-dioxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCSP([O-])([O-])=S AEXHGRVJDVETQU-UHFFFAOYSA-L 0.000 description 1
- GBEDXBRGRSPHRI-UHFFFAOYSA-L zinc;octoxy-octylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCOP([O-])(=S)SCCCCCCCC.CCCCCCCCOP([O-])(=S)SCCCCCCCC GBEDXBRGRSPHRI-UHFFFAOYSA-L 0.000 description 1
- HHMFJIHYTYQNJP-UHFFFAOYSA-L zinc;oxido-pentoxy-pentylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCOP([O-])(=S)SCCCCC.CCCCCOP([O-])(=S)SCCCCC HHMFJIHYTYQNJP-UHFFFAOYSA-L 0.000 description 1
- LZVDFWITYZHIEU-UHFFFAOYSA-L zinc;oxido-propoxy-propylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCOP([O-])(=S)SCCC.CCCOP([O-])(=S)SCCC LZVDFWITYZHIEU-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は圧縮機及び増速歯車装置を備えるタービン装置用潤滑油組成物に関する。 The present invention relates to a lubricating oil composition for a turbine device including a compressor and a speed increasing gear device .
近年の発電設備では、発電効率を高めエネルギーの有効活用のため、液化天然ガス（ＬＮＧ）等高温の燃焼ガスを用いるガスタービンや、ガスタービンと蒸気タービンとを組み合わせたコンバインドサイクル発電設備などが多くなってきている。この発電設備の場合、燃焼ガスの高温化に伴い使用するタービン油への熱負荷が大幅に増加している。
また、高炉生成ガス（ＢＦＧ）焚きコンバインドサイクル発電の場合、ＢＦＧは燃焼カロリーが低いので、発電効率を向上させる目的で、ＢＦＧを高度に昇圧する必要がある。そのためガスタービン−発電機−蒸気タービンにより構成する軸系と増速歯車装置を介して結合したガス圧縮機でＢＦＧを昇圧した後、ガスタービンに供給するようにする。
In recent power generation facilities, there are many gas turbines that use high-temperature combustion gases such as liquefied natural gas (LNG) and combined cycle power generation facilities that combine gas turbines and steam turbines in order to increase power generation efficiency and effectively use energy. It has become to. In the case of this power generation facility, the heat load on the turbine oil used is greatly increased as the combustion gas becomes hot.
Further, in the case of combined cycle power generation using blast furnace generated gas (BFG), BFG has low calorie calorie, so it is necessary to increase the pressure of BFG to a high degree in order to improve power generation efficiency. Therefore, after boosting the BFG with a gas compressor coupled via a speed increasing gear device and a shaft system constituted by a gas turbine-generator-steam turbine, the BFG is supplied to the gas turbine.
この増速歯車装置は、ガス圧縮機とタービン軸と発電機を直接連結しているが、タービン装置のコンパクト化を目的として、タービン軸受の潤滑油と増速歯車装置の潤滑油は兼用して使用できることが求められるようになってきた。このような潤滑油には、タービン油及びギヤ油としての双方の性能が要求され、歯車の耐摩耗性・極圧性が強く求められている。さらに、高い錆止め性が求められ、また高温且つ高面圧の過酷な条件下での優れた熱・酸化安定性及び耐スラッジ性能を有することが求められる。 In this speed increasing gear device, the gas compressor, the turbine shaft, and the generator are directly connected. For the purpose of downsizing the turbine device, the lubricating oil for the turbine bearing and the lubricating oil for the speed increasing gear device are combined. It has been required to be usable. Such a lubricating oil is required to have both performances as a turbine oil and a gear oil, and the wear resistance and extreme pressure property of the gear are strongly required. Furthermore, high rust prevention property is calculated | required, and it is calculated | required that it has the outstanding thermal and oxidation stability and sludge-proof performance on severe conditions of high temperature and high surface pressure.
こうしたことから、従来も、鉱油又は合成油にアルキル化ジフェニルアミン、アルキル化フェニル−α−ナフチルアミン、ベンゾトリアゾールを配合したガスタービン油が提案されているが、こうしたものでは、未だ充分な効果を得られないでいた。（特許文献１）
上記したように、従来の潤滑油は、上述の増速歯車装置を有するコンバインドサイクル発電のタービン軸受に使用した場合の耐スラッジ性能及び極圧性が必ずしも十分とは言えなかった。すなわち、高い防錆性、高い極圧性、耐摩耗性が要求される用途には、ジアルキルジチオリン酸亜鉛などの硫黄系極圧剤あるいはアルキル化チオフォスフェイトなどの硫黄−リン系極圧剤と防錆剤として、ＣａスルフォネートやＢａスルフォネート等を添加した潤滑油が広く使用されているが、防錆剤はその性質上、金属表面への吸着性に優れているため各種極圧剤の潤滑性能の向上作用を阻害する可能性が大きいので防錆性と極圧性を両立させるのは非常に難しい。 As described above, the conventional lubricating oil cannot always be said to have sufficient antisludge performance and extreme pressure resistance when used in a combined cycle power generation turbine bearing having the above-described speed increasing gear device. That is, for applications that require high rust prevention, high extreme pressure, and wear resistance, sulfur-based extreme pressure agents such as zinc dialkyldithiophosphates or sulfur-phosphorous extreme pressure agents such as alkylated thiophosphates may be used. Lubricating oils with added Ca sulfonate, Ba sulfonate, etc. are widely used as rusting agents. However, the antirusting agent is excellent in its ability to adsorb to the metal surface, and therefore has the lubricating performance of various extreme pressure agents. Since there is a high possibility of hindering the improvement action, it is very difficult to achieve both rust prevention and extreme pressure.
特に、潤滑剤が高温で使用される用途においては、硫黄系極圧剤はその添加量が微量であっても熱負荷が加わるとスラッジを多量に生成し、また熱安定性・酸化安定性を低下させる傾向がある。そのため、硫黄系極圧剤を添加した潤滑油では、上述の増速歯車装置を有するコンバインドサイクル発電のタービン軸受において十分な熱安定性・酸化安定性及び耐スラッジ性能を得ることが困難である。 In particular, in applications where lubricants are used at high temperatures, sulfur-based extreme pressure agents produce a large amount of sludge when a heat load is applied even if the amount added is very small, and also provide thermal stability and oxidation stability. There is a tendency to decrease. Therefore, it is difficult to obtain sufficient thermal stability, oxidation stability, and sludge resistance performance in a combined cycle power generation turbine bearing having the above-described speed increasing gear device with the lubricating oil to which the sulfur-based extreme pressure agent is added.
一方、リン系極圧剤は硫黄系極圧剤に比べてスラッジを生成しにくい傾向にあるが、リン系極圧剤を単独で使用した場合には、上記ギヤ油に要求される高いレベルの極圧性を得ることが困難である。 On the other hand, phosphorus-based extreme pressure agents tend to generate less sludge than sulfur-based extreme pressure agents. However, when a phosphorus-based extreme pressure agent is used alone, the high level required for the gear oil is high. It is difficult to obtain extreme pressure properties.
本発明は、このような実情に鑑みてなされたものであり、高温且つ高面圧の過酷な環境下で運転される増速歯車装置を有するコンバインドサイクル発電のタービン軸受などに使用した場合であっても、十分に長い酸化寿命を示し、高い錆止め性、高水準の耐スラッジ性、並びに高い極圧性を有している優良な潤滑油組成物を提供しようとするものである。 The present invention has been made in view of such circumstances, and is a case where it is used for a turbine bearing of a combined cycle power generation having a speed increasing gear device operated under a severe environment of high temperature and high surface pressure. However, it is an object of the present invention to provide an excellent lubricating oil composition that exhibits a sufficiently long oxidation life, has high rust prevention properties, high levels of sludge resistance, and high extreme pressure properties.
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、（ａ）鉱油及び合成油から選ばれる少なくとも１種の基油、（ｂ）コハク酸及び／又はそのエステルを０．０４質量％、（ｃ）グリシンの誘導体を０．００５〜０．０１質量％、（ｄ）リン化合物を含むリン系極圧剤、（ｅ）芳香族アミン化合物を含有させて圧縮機及び増速歯車装置を備えるタービン装置用潤滑油組成物とするもので、極圧性を阻害しやすい防錆剤の添加量を減少させ尚且つ優良な防錆性と、十分に長い酸化寿命を示し、尚且つ、高水準の耐スラッジ性、高い極圧性を得ることができる。 As a result of intensive studies to achieve the above object, the present inventors have obtained (a) at least one base oil selected from mineral oils and synthetic oils, and (b) succinic acid and / or esters thereof by 0.04. (C) 0.005 to 0.01% by mass of a glycine derivative, (d) a phosphorus extreme pressure agent containing a phosphorus compound, (e) a compressor and a speed increasing gear containing an aromatic amine compound A lubricating oil composition for a turbine device provided with a device, which reduces the addition amount of a rust preventive agent that tends to hinder extreme pressure properties, exhibits excellent rust prevention properties, and a sufficiently long oxidation life, and High level of sludge resistance and high extreme pressure can be obtained.
本発明の潤滑油組成物によれば、高温且つ高面圧の過酷な環境下で運転される増速歯車装置を有するコンバインドサイクル発電のタービン軸受などに、歯車と軸受の潤滑を兼用で使用した場合であっても、優良な錆止め性を得ることができる。また、潤滑油として十分に長い酸化寿命を示し、高水準の耐スラッジ性及び極圧性を達成することが可能となる。従って、本発明の潤滑油組成物は、増速歯車装置などにおける摺動部分の摩耗の抑制、焼付きの防止及びコンバインドサイクル発電等タービン軸受装置のメンテナンスインターバル延長の点で非常に有用である。 According to the lubricating oil composition of the present invention, the combined use of gears and bearings is used in a turbine bearing for combined cycle power generation having a speed increasing gear device that is operated under a severe environment of high temperature and high surface pressure. Even if it is a case, excellent rust prevention property can be obtained. Further, it exhibits a sufficiently long oxidation life as a lubricating oil, and can achieve a high level of sludge resistance and extreme pressure. Therefore, the lubricating oil composition of the present invention is very useful in terms of suppressing wear of sliding portions in speed-up gear devices, preventing seizure, and extending the maintenance interval of turbine bearing devices such as combined cycle power generation.
以下、本発明の好適な実施形態について詳細に説明する。なお、以下の説明において、化合物又は官能基が直鎖状及び分岐状の構造の双方を取り得る場合、特に断らない限り当該化合物には直鎖状のものと分岐状のものとの双方が含まれる。 Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description, when a compound or a functional group can take both a linear structure and a branched structure, the compound includes both a linear structure and a branched structure unless otherwise specified. It is.
本発明の潤滑油組成物は、鉱油、合成油から選ばれる少なくとも１種の基油を含有する。
鉱油としては、例えば、原油を常圧蒸留及び減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄、白土処理等の精製処理を適宜組み合わせて精製したパラフィン系、ナフテン系等の油を挙げることができる。
The lubricating oil composition of the present invention contains at least one base oil selected from mineral oil and synthetic oil.
As mineral oil, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing And oils such as paraffinic and naphthenic oils purified by appropriately combining purification treatments such as clay treatment.
合成油としては、例えば、ポリオレフィン、アルキルベンゼン、アルキルナフタレン、エステル、ポリオキシアルキレングリコール、ポリフェニルエーテル、ジアルキルジフェニルエーテル、含フッ素化合物（パーフルオロポリエーテル、フッ素化ポリオレフィン等）、シリコーン油などが挙げられる。
また、ワックス異性化油、ＧＴＬ ＷＡＸ（ガストゥリキッド ワックス）を異性化する手法で製造される基油等も使用可能である。
高度精製合成油としては、天然ガス（メタン等）のガス化プロセス（部分酸化）によって得られる水素と一酸化炭素を原料としてフィッシャートロプシュ重合にて重質直鎖パラフィンとし、これを前述と同様の接触分解異性化することで得られる粘度指数１３０以上（典型的には１４５〜１５５）を有する潤滑油基油で、ＧＴＬ（ガストゥリキッド）とも呼ばれる基油等を使用することも可能である。
Examples of the synthetic oil include polyolefin, alkylbenzene, alkylnaphthalene, ester, polyoxyalkylene glycol, polyphenyl ether, dialkyldiphenyl ether, fluorine-containing compounds (perfluoropolyether, fluorinated polyolefin, etc.), silicone oil and the like.
Further, it is also possible to use a wax isomerized oil, a base oil produced by a technique for isomerizing GTL WAX (gas-trimmed wax), and the like.
As highly refined synthetic oil, heavy linear paraffin is obtained by Fischer-Tropsch polymerization using hydrogen and carbon monoxide obtained by gasification process (partial oxidation) of natural gas (methane, etc.) as described above. A lubricating base oil having a viscosity index of 130 or more (typically 145 to 155) obtained by catalytic cracking isomerization, and a base oil called GTL (gas to liquid) can also be used.
これらの基油の中でも、より耐熱性、熱・酸化安定性に優れることから、水素化処理などを施して硫黄分含有量及び窒素含有量をできるだけ低減した鉱油、及び合成油のポリオレフィン、或いは、ＸＨＶＩ（登録商標）（ＧＴＬ（ガストゥリキッド））と呼ばれている合成油の使用が好ましい。 Among these base oils, because it is more excellent in heat resistance and thermal / oxidative stability, mineral oil and synthetic oil polyolefin, in which sulfur content and nitrogen content are reduced as much as possible by performing hydrogenation treatment, or The use of a synthetic oil called XHVI® (GTL (Gas Liquid)) is preferred.
上記ポリオレフィンには、各種オレフィンの重合物、又はこれらの水素化物が含まれる。オレフィンとしては任意のものが用いられるが、例えば、エチレン、プロピレン、ブテン（１−ブテン、２−ブテン、イソブテン）、炭素数５以上のα−オレフィンなどが挙げられる。ポリオレフィンの製造にあたっては、上記オレフィンの１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The polyolefin includes polymers of various olefins or hydrides thereof. Any olefin may be used, and examples thereof include ethylene, propylene, butene (1-butene, 2-butene, isobutene), α-olefin having 5 or more carbon atoms, and the like. In the production of polyolefin, one of the above olefins may be used alone, or two or more may be used in combination.
本発明の潤滑油組成物における上記基油の含有量は特に制限されないが、潤滑油組成物の全量基準で、６０質量％以上、好ましくは７０質量％以上、より好ましくは８０質量％以上、更に好ましくは９０質量％以上である。 The content of the base oil in the lubricating oil composition of the present invention is not particularly limited, but is 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, based on the total amount of the lubricating oil composition. Preferably it is 90 mass% or more.
上記基油の粘度は特に制限されないが、４０℃における動粘度は、好ましくは２〜６８０ｍｍ２／ｓ、より好ましくは８〜２２０ｍｍ２／ｓである。
また、全硫黄分は、０〜１００ｐｐｍ、好ましくは０〜３０ｐｐｍがよい。
全窒素分も０〜１００ｐｐｍ、好ましくは０〜３０ｐｐｍがよい。
さらに、アニリン点は８０〜１５０℃、好ましくは１１０〜１３５℃のものを使用するとよい。
The viscosity of the base oil is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 2 to 680 mm 2 / s, more preferably 8 to 220 mm 2 / s.
The total sulfur content is 0 to 100 ppm, preferably 0 to 30 ppm.
The total nitrogen content is also 0 to 100 ppm, preferably 0 to 30 ppm.
Furthermore, the aniline point may be 80 to 150 ° C, preferably 110 to 135 ° C.
上記基油には、コハク酸及び／又はそのエステル、グリシンの誘導体、リン系極圧剤、芳香族アミン化合物を含有させて圧縮機及び増速歯車装置を備えるタービン装置用潤滑油組成物にする。
上記コハク酸及び／又はそのエステルは、下記式１に示すコハク酸及び／又は炭素数１〜３０のアルコールとの部分エステルである。
The above base oil contains a succinic acid and / or ester thereof, a glycine derivative, a phosphorus extreme pressure agent, and an aromatic amine compound to form a lubricating oil composition for a turbine device including a compressor and a speed increasing gear device. .
The succinic acid and / or ester thereof is a partial ester with succinic acid and / or an alcohol having 1 to 30 carbon atoms shown in the following formula 1.
また、上記グリシンの誘導体は、下記式２に示すグリシンの誘導体である。 The glycine derivative is a glycine derivative represented by the following formula 2.
上記式２に示すグリシンの誘導体としては、具体的には、例えば、下記の式３の（Ｚ）−Ｎ−メチル−Ｎ−（１−オキソ−９−オクタデセニル）グリシンなどが、挙げられる。 Specific examples of the glycine derivative represented by the above formula 2 include (Z) -N-methyl-N- (1-oxo-9-octadecenyl) glycine represented by the following formula 3.
上記コハク酸及び／又はそのエステルは、圧縮機及び増速歯車装置を備えるタービン装置用潤滑油組成物の全量に対して、０．０４〜０．１質量％含有するように使用される。また、上記グリシンの誘導体は、同じく０．００５〜０．０１質量％含有するように使用される。
そして、コハク酸及び／又はそのエステルとグリシンの誘導体の質量比は、１：０．０１〜０．７、好ましくは１：０．０２〜０．５、より好ましくは１：０．０５〜０．３となるように使用するのが良い。
The succinic acid and / or ester thereof is used so as to be contained in an amount of 0.04 to 0.1% by mass with respect to the total amount of the lubricating oil composition for a turbine device including a compressor and a speed increasing gear device . Further, derivatives of the glycine is used to contain also from 0.005 to 0.01 wt%.
The mass ratio of succinic acid and / or its ester and glycine derivative is 1: 0.01 to 0.7, preferably 1: 0.02 to 0.5, more preferably 1: 0.05 to 0. .3 should be used.
この潤滑油組成物には、さらに極圧性の向上のためにリン化合物を含有させることが好ましい。
このリン化合物としては、リン酸エステル、酸性リン酸エステル、酸性リン酸エステルのアミン塩、塩素化リン酸エステル、亜リン酸エステル、ホスフォロチオネート、ジチオリン酸亜鉛、ジチオリン酸エステル或いはその誘導体、リン含有カルボン酸、またはリン含有カルボン酸エステルの少なくとも１種、またはこれらの混合物があり、熱・酸化安定性の点から好ましく用いられる。
This lubricating oil composition preferably further contains a phosphorus compound in order to improve extreme pressure.
As this phosphorus compound, phosphate ester, acidic phosphate ester, amine salt of acidic phosphate ester, chlorinated phosphate ester, phosphite ester, phosphorothionate, zinc dithiophosphate, dithiophosphate ester or derivatives thereof, There are at least one phosphorus-containing carboxylic acid, phosphorus-containing carboxylic acid ester, or a mixture thereof, which is preferably used from the viewpoint of thermal and oxidation stability.
リン酸エステルとしては、具体的には、例えば、トリブチルホスフェート、トリペンチルホスフェート、トリヘキシルホスフェート、トリヘプチルホスフェート、トリオクチルホスフェート、トリノニルホスフェート、トリデシルホスフェート、トリウンデシルホスフェート、トリドデシルホスフェート、トリトリデシルホスフェート、トリテトラデシルホスフェート、トリペンタデシルホスフェート、トリヘキサデシルホスフェート、トリヘプタデシルホスフェート、トリオクタデシルホスフェート、トリオレイルホスフェート、トリフェニルホスフェート、トリス（ｉｓｏ−プロピルフェニル）ホスフェート、トリアリールホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、及びキシレニルジフェニルホスフェートなどが挙げられる。 Specific examples of phosphate esters include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate. Decyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tris (iso-propylphenyl) phosphate, triaryl phosphate, tricres Zyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and Such xylenyl diphenyl phosphate and the like.
酸性リン酸エステルの具体例としては、モノブチルアシッドホスフェート、モノペンチルアシッドホスフェート、モノヘキシルアシッドホスフェート、モノヘプチルアシッドホスフェート、モノオクチルアシッドホスフェート、モノノニルアシッドホスフェート、モノデシルアシッドホスフェート、モノウンデシルアシッドホスフェート、モノドデシルアシッドホスフェート、モノトリデシルアシッドホスフェート、モノテトラデシルアシッドホスフェート、モノペンタデシルアシッドホスフェート、モノヘキサデシルアシッドホスフェート、モノヘプタデシルアシッドホスフェート、モノオクタデシルアシッドホスフェート、モノオレイルアシッドホスフェート、ジブチルアシッドホスフェート、ジペンチルアシッドホスフェート、ジヘキシルアシッドホスフェート、ジヘプチルアシッドホスフェート、ジオクチルアシッドホスフェート、ジノニルアシッドホスフェート、ジデシルアシッドホスフェート、ジウンデシルアシッドホスフェート、ジドデシルアシッドホスフェート、ジトリデシルアシッドホスフェート、ジテトラデシルアシッドホスフェート、ジペンタデシルアシッドホスフェート、ジヘキサデシルアシッドホスフェート、ジヘプタデシルアシッドホスフェート、ジオクタデシルアシッドホスフェート、及びジオレイルアシッドホスフェートなどが挙げられる。 Specific examples of the acidic phosphate ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate , Monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate Dipentyl acid phosphate, dihexyl Ruacid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl phosphate, dipentadecyl phosphate Examples include dihexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, and dioleyl acid phosphate.
酸性リン酸エステルのアミン塩としては、前記酸性リン酸エステルのメチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジヘプチルアミン、ジオクチルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、トリヘプチルアミン、及びトリオクチルアミンなどのアミンとの塩が挙げられる。 Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Examples include salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, and trioctylamine.
塩素化リン酸エステルとしては、トリス・ジクロロプロピルホスフェート、トリス・クロロエチルホスフェート、トリス・クロロフェニルホスフェート、及びポリオキシアルキレン・ビス［ジ（クロロアルキル）］ホスフェートなどが挙げられる。 Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, and polyoxyalkylene bis [di (chloroalkyl)] phosphate.
亜リン酸エステルとしては、ジブチルホスファイト、ジペンチルホスファイト、ジヘキシルホスファイト、ジヘプチルホスファイト、ジオクチルホスファイト、ジノニルホスファイト、ジデシルホスファイト、ジウンデシルホスファイト、ジドデシルホスファイト、ジオレイルホスファイト、ジフェニルホスファイト、ジクレジルホスファイト、トリブチルホスファイト、トリペンチルホスファイト、トリヘキシルホスファイト、トリヘプチルホスファイト、トリオクチルホスファイト、トリノニルホスファイト、トリデシルホスファイト、トリウンデシルホスファイト、トリドデシルホスファイト、トリオレイルホスファイト、トリフェニルホスファイト、及びトリクレジルホスファイトなどが挙げられる。 As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite and the like can be mentioned.
また、ホスフォロチオネートとしては、具体的には、トリブチルホスフォロチオネート、トリペンチルホスフォロチオネート、トリヘキシルホスフォロチオネート、トリヘプチルホスフォロチオネート、トリオクチルホスフォロチオネート、トリノニルホスフォロチオネート、トリデシルホスフォロチオネート、トリウンデシルホスフォロチオネート、トリドデシルホスフォロチオネート、トリトリデシルホスフォロチオネート、トリテトラデシルホスフォロチオネート、トリペンタデシルホスフォロチオネート、トリヘキサデシルホスフォロチオネート、トリヘプタデシルホスフォロチオネート、トリオクタデシルホスフォロチオネート、トリオレイルホスフォロチオネート、トリフェニルホスフォロチオネート、トリクレジルホスフォロチオネート、トリキシレニルホスフォロチオネート、クレジルジフェニルホスフォロチオネート、キシレニルジフェニルホスフォロチオネート、トリス（ｎ−プロピルフェニル）ホスフォロチオネート、トリス（イソプロピルフェニル）ホスフォロチオネート、トリス（ｎ−ブチルフェニル）ホスフォロチオネート、トリス（イソブチルフェニル）ホスフォロチオネート、トリス（ｓ−ブチルフェニル）ホスフォロチオネート、トリス（ｔ−ブチルフェニル）ホスフォロチオネート等、が挙げられる。また、これらの混合物も使用できる。 Specific examples of the phosphorothioate include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl. Phosphorothioate, tridecyl phosphorothionate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tritridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, Trihexadecyl phosphorothioate, triheptadecyl phosphorothionate, trioctadecyl phosphorothionate, trioleyl phosphorothionate, triphenyl phosphorothionate, tricresyl phosphorothio Onate, trixylenyl phosphorothioate, cresyl diphenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phosphorothionate, tris (N-butylphenyl) phosphorothionate, tris (isobutylphenyl) phosphorothionate, tris (s-butylphenyl) phosphorothionate, tris (t-butylphenyl) phosphorothionate, and the like. Mixtures of these can also be used.
ジチオリン酸亜鉛としては、一般に、ジアルキルジチオリン酸亜鉛、ジアリールジチオリン酸亜鉛、アリールアルキルジチオリン酸亜鉛等が挙げられる。
例えば、ジアルキルジチオリン酸亜鉛のアルキル基は、炭素数３〜２２の第１級又は第２級のアルキル基、炭素数３〜１８のアルキル基で置換されたアルキルアリール基を有するジアルキルジチオリン酸亜鉛が使用される。
ジアルキルジチオリン酸亜鉛の具体例としては、ジプロピルジチオリン酸亜鉛、ジブチルジチオリン酸亜鉛、ジペンチルジチオリン酸亜鉛、ジヘキシルジチオリン酸亜鉛、ジイソペンチルジチオリン酸亜鉛、ジエチルヘキシルジチオリン酸亜鉛、ジオクチルジチオリン酸亜鉛、ジノニルジチオリン酸亜鉛、ジデシルジチオリン酸亜鉛、ジドデシルジチオリン酸亜鉛、ジプロピルフェニルジチオリン酸亜鉛、ジペンチルフェニルジチオリン酸亜鉛、ジプロピルメチルフェニルジチオリン酸亜鉛、ジノニルフェニルジチオリン酸亜鉛、ジドデシルフェニルジチオリン酸亜鉛、等が挙げられる。
Examples of zinc dithiophosphate generally include zinc dialkyldithiophosphate, zinc diaryldithiophosphate, zinc arylalkyldithiophosphate, and the like.
For example, the zinc group of zinc dialkyldithiophosphate is a zinc dialkyldithiophosphate having an alkylaryl group substituted with a primary or secondary alkyl group having 3 to 22 carbon atoms or an alkyl group having 3 to 18 carbon atoms. used.
Specific examples of zinc dialkyldithiophosphate include zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophosphate, zinc dihexyldithiophosphate, zinc diisopentyldithiophosphate, zinc diethylhexyldithiophosphate, zinc dioctyldithiophosphate, Zinc nonyldithiophosphate, zinc didecyldithiophosphate, zinc didodecyldithiophosphate, zinc dipropylphenyldithiophosphate, zinc dipentylphenyldithiophosphate, zinc dipropylmethylphenyldithiophosphate, zinc dinonylphenyldithiophosphate, didodecylphenyldithiophosphate Zinc and the like.
ジチオリン酸エステル或いはその誘導体としては以下のものが挙げられる。
モノプロピルジチオホスフェート、モノブチルジチオホスフェート、モノペンチルジチオホスフェート、モノヘキシルジチオホスフェート、モノペプチルジチオホスフェート、モノオクチルジチオホスフェート、モノラウリルジチオホスフェート等のジチオリン酸
モノアルキルエステル（アルキル基は直鎖状でも分枝状でもよい）；モノフェニルジチオホスフェート、モノクレジルジチオホスフェート等のジチオリン酸モノ（（アルキル）アリール）エステル；ジプロピルジチオホスフェート、ジブチルジチオホスフェート、ジペンチルジチオホスフェート、ジヘキシルジチオホスフェート、ジヘプチルジチオホスフェート、ジオクチルジチオホスフェート、ジラウリルジチオホスフェート等のジチオリン酸ジアルキルエステル（アルキル基は直鎖状でも分枝状でもよい）；ジフェニルジチオホスフェート、ジクレジルジチオホスフェート等のジチオリン酸ジ（（アルキル）アリール）エステル；トリプロピルジチオホスフェート、トリブチルジチオホスフェート、トリペンチルジチオホスフェート、トリヘキシルジチオホスフェート、トリヘプチルジチオホスフェート、トリオクチルジチオホスフェート、トリラウリルジチオホスフェート等のジチオリン酸トリアルキルエステル（アルキル基は直鎖状でも分枝状でもよい）；トリフェニルジチオホスフェート、トリクレジルジチオホスフェート等のジチオリン酸トリ（（アルキル）アリール）エステルなどが例示できる。
Examples of dithiophosphoric acid esters or derivatives thereof include the following.
Dithiophosphoric acid monoalkyl esters such as monopropyldithiophosphate, monobutyldithiophosphate, monopentyldithiophosphate, monohexyldithiophosphate, monopeptyldithiophosphate, monooctyldithiophosphate, monolauryldithiophosphate May be branched); dithiophosphoric acid mono ((alkyl) aryl) esters such as monophenyldithiophosphate, monocresyldithiophosphate; dipropyldithiophosphate, dibutyldithiophosphate, dipentyldithiophosphate, dihexyldithiophosphate, diheptyldithio Dithiophosphoric acid dialkyl esters (alkyl group) such as phosphate, dioctyl dithiophosphate, dilauryl dithiophosphate Linear or branched); dithiophosphoric acid di ((alkyl) aryl) esters such as diphenyldithiophosphate, dicresyldithiophosphate; tripropyldithiophosphate, tributyldithiophosphate, tripentyldithiophosphate, trihexyldithiophosphate Dithiophosphoric acid trialkyl esters such as triheptyl dithiophosphate, trioctyl dithiophosphate, trilauryl dithiophosphate (the alkyl group may be linear or branched); dithiolin such as triphenyldithiophosphate, tricresyl dithiophosphate, etc. Examples include acid tri ((alkyl) aryl) esters.
また、リン含有カルボン酸化合物としては、同一分子中にカルボキシル基とリン原子の双方を含んでいればよく、その構造は特に制限されない。しかし、極圧性及び熱・酸化安定性の点から、ホスホリル化カルボン酸、若しくは、ホスホリル化カルボン酸エステルが好ましい。 The phosphorus-containing carboxylic acid compound is not particularly limited as long as it contains both a carboxyl group and a phosphorus atom in the same molecule. However, phosphorylated carboxylic acid or phosphorylated carboxylic acid ester is preferable from the viewpoint of extreme pressure and heat / oxidation stability.
ホスホリル化カルボン酸及びホスホリル化カルボン酸エステルとしては、例えば下記の式４で表される化合物が挙げられる。 Examples of phosphorylated carboxylic acid and phosphorylated carboxylic acid ester include compounds represented by the following formula 4.
上記式４中の、Ｒ4及びＲ5はそれぞれ水素原子又は炭素数１〜３０の炭化水素基を表しているが、炭素数１〜３０の炭化水素基としては、アルキル基、アルケニル基、アリール基、アルキルアリール基、アリールアルキル基等が挙げられる。 In the above formula 4, R4 and R5 each represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an aryl group, An alkylaryl group, an arylalkyl group, etc. are mentioned.
上記ホスホリル化カルボン酸の中でも有用なβ−ジチオホスホリル化プロピオン酸としては、下記の式５の構造を有するものである。 Among the phosphorylated carboxylic acids, useful β-dithiophosphorylated propionic acid has a structure of the following formula 5.
このβ−ジチオホスホリル化プロピオン酸としては、具体的に、３−（ジ−イソブトキシ−チオホスホリルスルファニル）−２−メチル−プロピオン酸などが挙げられる。 Specific examples of the β-dithiophosphorylated propionic acid include 3- (di-isobutoxy-thiophosphorylsulfanyl) -2-methyl-propionic acid.
本潤滑油組成物におけるリン含有カルボン酸化合物の含有量は、特に制限されるものではないが、潤滑油組成物の全量基準で、好ましくは０．００１〜１質量％、より好ましくは０．００２〜０．５質量％である。
リン含有カルボン酸化合物の含有量が前記下限値未満では十分な潤滑性が得られない傾向にある。一方、前記上限値を超えても含有量に見合う潤滑性向上効果が得られない傾向にあり、更には熱・酸化安定性や加水分解安定性が低下するおそれがあるので好ましくない。
The content of the phosphorus-containing carboxylic acid compound in the present lubricating oil composition is not particularly limited, but is preferably 0.001 to 1% by mass, more preferably 0.002 based on the total amount of the lubricating oil composition. It is -0.5 mass%.
If the content of the phosphorus-containing carboxylic acid compound is less than the lower limit, sufficient lubricity tends to be not obtained. On the other hand, even if the upper limit is exceeded, there is a tendency that an effect of improving lubricity commensurate with the content tends not to be obtained, and furthermore, heat / oxidation stability and hydrolysis stability may be lowered.
なお、上記式（４）で表されるホスホリル化カルボン酸のうち、Ｒ7が水素原子である化合物の含有量については、好ましくは０．００１〜０．１質量％、より好ましくは０．００２〜０．０８質量％、更に好ましくは０．００３〜０．０７質量％、一層好ましくは０．００４〜０．０６質量％、特に好ましくは０．００５〜０．０５質量％である。
当該含有量が０．００１質量％未満の場合は極圧性向上効果が不十分となるおそれがあり、一方、０．１質量％を超えると熱・酸化安定性が低下するおそれがある。
In addition, about content of the compound whose R7 is a hydrogen atom among the phosphorylated carboxylic acid represented by the said Formula (4), Preferably it is 0.001-0.1 mass%, More preferably, it is 0.002-. It is 0.08 mass%, More preferably, it is 0.003-0.07 mass%, More preferably, it is 0.004-0.06 mass%, Most preferably, it is 0.005-0.05 mass%.
If the content is less than 0.001% by mass, the effect of improving extreme pressure may be insufficient. On the other hand, if it exceeds 0.1% by mass, the thermal / oxidation stability may be lowered.
上記のリン化合物の中でも、より極圧性等の諸性能に優れることから、リン酸エステル、酸性リン酸エステル、酸性リン酸エステルのアミン塩、塩素化リン酸エステル、亜リン酸エステル及びホスフォロチオネート、β−ジチオホスホリル化プロピオン酸が好ましく、リン酸エステル、β−ジチオホスホリル化プロピオン酸がより好ましく、トリフェニルホスフェート、トリクレジルホスフェート、モノクレジルジフェニルホスフェート、ジクレジルモノフェニルホスフェート等のトリアリールホスフェート、β−ジチオホスホリル化プロピオン酸が更により好ましい。 Among the above-mentioned phosphorus compounds, phosphoric acid ester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, chlorinated phosphoric acid ester, phosphorous acid ester and phosphorothioate are superior in various performances such as extreme pressure. Nate and β-dithiophosphorylated propionic acid are preferred, phosphate ester and β-dithiophosphorylated propionic acid are more preferred, and triphenyl phosphate, tricresyl phosphate, monocresyl diphenyl phosphate, dicresyl monophenyl phosphate, etc. Even more preferred are reel phosphate, β-dithiophosphorylated propionic acid.
上記リン化合物の含有量は特に制限されないが、潤滑油組成物の全量基準で、好ましくは０．０１〜５質量％、より好ましくは０．０５〜４．５質量％、更に好ましくは０．１〜４質量％、一層好ましくは０．５〜３．５質量％、特に好ましくは１〜３質量％である。リン化合物の含有量が０．０１質量％未満の場合はリン化合物の含有による極圧性向上効果が不十分となるおそれがあり、一方、５質量％を超えると熱・酸化安定性及び泡立ち性が低下するおそれがある。 The content of the phosphorus compound is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.05 to 4.5% by mass, and still more preferably 0.1% based on the total amount of the lubricating oil composition. It is -4 mass%, More preferably, it is 0.5-3.5 mass%, Most preferably, it is 1-3 mass%. If the phosphorus compound content is less than 0.01% by mass, the effect of improving the extreme pressure due to the phosphorus compound content may be insufficient. May decrease.
この潤滑油組成物には、更に芳香族アミン化合物を含ませることができ、こうした芳香族アミン化合物としては、フェニル−α−ナフチルアミン系化合物、ジアルキルジフェニルアミン系化合物が挙げられる。 This lubricating oil composition may further contain an aromatic amine compound, and examples of such aromatic amine compounds include phenyl-α-naphthylamine compounds and dialkyldiphenylamine compounds.
フェニル−α−ナフチルアミン系化合物としては、下記一般式６で表されるフェニル−α−ナフチルアミンが好ましく用いられる。 As the phenyl-α-naphthylamine compound, phenyl-α-naphthylamine represented by the following general formula 6 is preferably used.
上記式６中のＲ1がアルキル基である場合、このアルキル基は炭素数１〜１６の直鎖状又は分岐状のものである。このようなアルキル基としては、具体的には、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、及びヘキサデシル等が挙げられる。なお、Ｒ1の炭素数が１６を超える場合には、分子中に占める官能基の割合が小さくなり、酸化防止性能に悪影響を与える恐れがある。 When R1 in the above formula 6 is an alkyl group, the alkyl group is linear or branched having 1 to 16 carbon atoms. Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl. It is done. When the number of carbon atoms in R1 exceeds 16, the proportion of functional groups in the molecule is reduced, which may adversely affect the antioxidant performance.
一般式６中のＲ1がアルキル基である場合、溶解性に優れる点から、Ｒ1は、炭素数８〜１６の分枝アルキル基が好ましく、さらに炭素数３又は４のオレフィンのオリゴマーから誘導される炭素数８〜１６の分枝アルキル基がより好ましい。炭素数３又は４のオレフィンとしては、具体的には、プロピレン、１−ブテン、２−ブテン及びイソブチレンが挙げられるが、溶解性の点から、プロピレン又はイソブチレンが好ましい。
更に優れた溶解性を得るためには、Ｒ1は、イソブチレンの２量体から誘導される分枝オクチル基、プロピレンの３量体から誘導される分枝ノニル基、イソブチレンの３量体から誘導される分枝ドデシル基、プロピレンの４量体から誘導される分枝ドデシル基又はプロピレンの５量体から誘導される分枝ペンタデシル基がさらにより好ましく、イソブチレンの２量体から誘導される分枝オクチル基、イソブチレンの３量体から誘導される分枝ドデシル基又はプロピレンの４量体から誘導される分枝ドデシル基が特に好ましい。
When R1 in the general formula 6 is an alkyl group, from the viewpoint of excellent solubility, R1 is preferably a branched alkyl group having 8 to 16 carbon atoms, and further derived from an oligomer of an olefin having 3 or 4 carbon atoms. A branched alkyl group having 8 to 16 carbon atoms is more preferable. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene and isobutylene, and propylene or isobutylene is preferable from the viewpoint of solubility.
In order to obtain better solubility, R1 is derived from a branched octyl group derived from a dimer of isobutylene, a branched nonyl group derived from a trimer of propylene, or a trimer of isobutylene. Even more preferred are branched dodecyl groups, branched dodecyl groups derived from propylene tetramers, or branched pentadecyl groups derived from propylene pentamers, and branched octyl derived from isobutylene dimers. Particularly preferred are branched dodecyl groups derived from the trimer of the group isobutylene or branched dodecyl groups derived from the tetramer of propylene.
また、Ｒ1がアルキル基である場合、フェニル基の任意の位置に結合可能であるがアミノ基に対してｐ−位であることが好ましい。更に、アミノ基はナフチル基の任意の位置に結合可能であるが、α位であることが好ましい。 When R1 is an alkyl group, it can be bonded to any position of the phenyl group, but is preferably p-position to the amino group. Furthermore, the amino group can be bonded to any position of the naphthyl group, but is preferably in the α position.
上記一般式（６）で表されるフェニル−α−ナフチルアミンとしては、市販のものを用いても良く、また合成物を用いても良い。合成物は、フリーデル・クラフツ触媒を用いて、フェニル−α−ナフチルアミンと炭素数１〜１６のハロゲン化アルキル化合物との反応、あるいはフェニル−α−ナフチルアミンと炭素数２〜１６のオレフィン又は炭素数２〜１６のオレフィンオリゴマーとの反応を行うことにより容易に合成することができる。フリーデル・クラフツ触媒としては、具体的には例えば、塩化アルミニウム、塩化亜鉛、塩化鉄等の金属ハロゲン化物；硫酸、リン酸、五酸化リン、フッ化ホウ素、酸性白土、活性白土等の酸性触媒；等を用いることができる。 As phenyl-α-naphthylamine represented by the general formula (6), a commercially available product may be used, or a synthesized product may be used. The synthesized product is a reaction between phenyl-α-naphthylamine and a halogenated alkyl compound having 1 to 16 carbon atoms, or phenyl-α-naphthylamine and an olefin or carbon number having 2 to 16 carbon atoms, using a Friedel-Crafts catalyst. It can be easily synthesized by reacting with 2 to 16 olefin oligomers. Specific examples of Friedel-Crafts catalysts include metal halides such as aluminum chloride, zinc chloride, and iron chloride; acidic catalysts such as sulfuric acid, phosphoric acid, phosphorus pentoxide, boron fluoride, acidic clay, and activated clay. Etc. can be used.
また、ジアルキルジフェニルアミン系化合物としては、下記式７で表されるジアルキルジフェニルアミンが好ましく用いられる。 Moreover, as a dialkyl diphenylamine type compound, the dialkyl diphenylamine represented by following formula 7 is used preferably.
このＲ2及びＲ3で表されるアルキル基としては、具体的には、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル等（これらのアルキル基は直鎖状でも分枝状でも良い）が挙げられる。
これらの中でも、溶解性に優れる点から、Ｒ2及びＲ3としては、炭素数３〜１６の分枝アルキル基が好ましく、炭素数３又は４のオレフィン又はそのオリゴマーから誘導される炭素数３〜１６の分枝アルキル基がより好ましい。炭素数３又は４のオレフィンとしては、具体的にはプロピレン、１−ブテン、２−ブテン及びイソブチレン等が挙げられるが、溶解性に優れる点から、プロピレン又はイソブチレンが好ましい。
Specific examples of the alkyl group represented by R2 and R3 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, etc. (These alkyl groups may be linear or branched).
Among these, from the point of being excellent in solubility, as R2 and R3, a branched alkyl group having 3 to 16 carbon atoms is preferable, and a group having 3 to 16 carbon atoms derived from an olefin having 3 or 4 carbon atoms or an oligomer thereof. A branched alkyl group is more preferred. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene, and isobutylene, but propylene or isobutylene is preferable from the viewpoint of excellent solubility.
また、Ｒ2又はＲ3としては、更に優れた溶解性が得られることから、それぞれプロピレンから誘導されるイソプロピル基、イソブチレンから誘導されるｔｅｒｔ−ブチル基、プロピレンの２量体から誘導される分枝ヘキシル基、イソブチレンの２量体から誘導される分枝オクチル基、プロピレンの３量体から誘導される分枝ノニル基、イソブチレンの３量体から誘導される分枝ドデシル基、プロピレンの４量体から誘導される分枝ドデシル基又はプロピレンの５量体から誘導される分枝ペンタデシル基がさらにより好ましく、イソブチレンから誘導されるｔｅｒｔ−ブチル基、プロピレンの２量体から誘導される分枝ヘキシル基、イソブチレンの２量体から誘導される分枝オクチル基、プロピレンの３量体から誘導される分枝ノニル基、イソブチレンの３量体から誘導される分枝ドデシル基又はプロピレンの４量体から誘導される分枝ドデシル基が最も好ましい。 Further, as R2 or R3, further excellent solubility can be obtained, so that an isopropyl group derived from propylene, a tert-butyl group derived from isobutylene, and a branched hexyl derived from a dimer of propylene, respectively. Group, branched octyl group derived from isobutylene dimer, branched nonyl group derived from propylene trimer, branched dodecyl group derived from isobutylene trimer, propylene tetramer Even more preferred are branched dodecyl groups derived or branched pentadecyl groups derived from pentamers of propylene, tert-butyl groups derived from isobutylene, branched hexyl groups derived from propylene dimers, A branched octyl group derived from a dimer of isobutylene, a branched nonyl group derived from a trimer of propylene, A branched dodecyl group derived from a tetramer of branched dodecyl or propylene derived from a trimer of styrene is most preferred.
なお、Ｒ2又はＲ3の一方又は双方が水素原子である化合物を用いると、当該化合物自体の酸化によりスラッジが発生する恐れがある。また、アルキル基の炭素数が１６を超える場合には、分子中に占める官能基の割合が小さくなり、高温での酸化防止性が低下する恐れがある。 When a compound in which one or both of R2 and R3 are hydrogen atoms is used, sludge may be generated due to oxidation of the compound itself. Moreover, when the number of carbon atoms of the alkyl group exceeds 16, the proportion of the functional group in the molecule becomes small, and the antioxidant property at high temperature may be lowered.
Ｒ2又はＲ3で示されるアルキル基は、それぞれフェニル基の任意の位置に結合可能であるが、アミノ基に対してｐ−位であることが好ましく、すなわち上記式７で表されるジアルキルジフェニルアミンはｐ，ｐ’−ジアルキルジフェニルアミンであることが好ましい。 The alkyl group represented by R2 or R3 can be bonded to any position of the phenyl group, but is preferably p-position with respect to the amino group, that is, the dialkyldiphenylamine represented by the above formula 7 is p-position. , P′-dialkyldiphenylamine is preferred.
上記の式７で表されるジアルキルジフェニルアミンは市販のものを用いても良く、また合成物を用いても良い。合成物は、フリーデル・クラフツ触媒を用い、ジフェニルアミンと炭素数１〜１６のハロゲン化アルキル化合物との反応、あるいはジフェニルアミンと炭素数２〜１６のオレフィン又は炭素数２〜１６のオレフィン又はこれらのオリゴマーとの反応を行うことにより容易に合成することができる。フリーデル・クラフツ触媒としては、フェニル−α−ナフチルアミン系化合物の説明において例示した金属ハロゲン化物や酸性触媒等が用いられる。 A commercially available dialkyldiphenylamine represented by the above formula 7 may be used, or a synthetic product may be used. The synthesized product is a reaction between diphenylamine and an alkyl halide having 1 to 16 carbon atoms using Friedel-Crafts catalyst, or diphenylamine and an olefin having 2 to 16 carbon atoms, an olefin having 2 to 16 carbon atoms or an oligomer thereof. It can synthesize | combine easily by performing reaction with. As the Friedel-Crafts catalyst, metal halides and acidic catalysts exemplified in the description of the phenyl-α-naphthylamine-based compound are used.
上記式（６）、（７）で表される芳香族アミン化合物は１種を単独で用いても良いし、構造の異なる２種以上の混合物を用いても良いが、高温での酸化防止性をより長期にわたって維持できることから、式（６）で表されるフェニル−α−ナフチルアミンと式（７）で表されるジアルキルジフェニルアミンとを併用することが好ましい。この場合の混合比は任意であるが、質量比で１／１０〜１０／１の範囲にあることが好ましい。 As the aromatic amine compounds represented by the above formulas (6) and (7), one kind may be used alone, or two or more kinds of mixtures having different structures may be used. Therefore, it is preferable to use a phenyl-α-naphthylamine represented by formula (6) and a dialkyldiphenylamine represented by formula (7) in combination. The mixing ratio in this case is arbitrary, but is preferably in the range of 1/10 to 10/1 by mass ratio.
また、本発明の潤滑油組成物中の芳香族アミン化合物合計の含有量は特に制限されないが、潤滑油組成物の全量基準で、好ましくは０．０１〜５質量％、より好ましくは０．０２〜４質量％、更に好ましくは０．０３〜３質量％、更により好ましくは０．０４〜２質量％、特に好ましくは０．０５〜１質量％である。合計の含有量が０．０１質量％未満の場合には酸化安定性や熱安定性が不十分となる傾向にある。一方、５質量％を超える場合には、含有量に見合う酸化安定性の効果が得られず、更にはスラッジの増加の原因となるため好ましくない。 The total content of aromatic amine compounds in the lubricating oil composition of the present invention is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.02 based on the total amount of the lubricating oil composition. It is -4 mass%, More preferably, it is 0.03-3 mass%, More preferably, it is 0.04-2 mass%, Most preferably, it is 0.05-1 mass%. When the total content is less than 0.01% by mass, the oxidation stability and thermal stability tend to be insufficient. On the other hand, if it exceeds 5% by mass, the effect of oxidation stability commensurate with the content cannot be obtained, and further, it causes an increase in sludge, which is not preferable.
本発明の潤滑油組成物には、更にその各種性能を高める目的で、公知の潤滑油添加剤の１種を単独で、又は２種以上を組み合わせて使用することができる。かかる添加剤としては、例えば、フェノール系、フェノチアジン系等の酸化防止剤；ポリアクリレート等のアクリレート系又はアルキルポリシロキサン等のシロキサン系などの消泡剤；ベンゾトリアゾール又はその誘導体等の金属不活性化剤；ポリメタクリレート、ポリイソブチレン、オレフィンコポリマー、ポリスチレン等の流動点降下剤などが挙げられる。
これらの添加剤を用いる場合の含有量は任意であるが、組成物全量基準で、酸化防止剤の場合は０．１〜５質量％、消泡剤の場合は０．０００５〜１質量％、金属不活性化剤の場合は０．００５〜１質量％、その他の添加剤の場合はそれぞれ０．１〜１５質量％が好ましい。
In the lubricating oil composition of the present invention, one kind of known lubricating oil additives can be used alone or in combination of two or more kinds for the purpose of further enhancing various performances. Examples of such additives include antioxidants such as phenols and phenothiazines; antifoaming agents such as acrylates such as polyacrylates or siloxanes such as alkylpolysiloxanes; metal deactivation such as benzotriazole or its derivatives Agents; pour point depressants such as polymethacrylate, polyisobutylene, olefin copolymer, polystyrene and the like.
The content in the case of using these additives is arbitrary, but based on the total amount of the composition, 0.1 to 5% by mass in the case of an antioxidant, 0.0005 to 1% by mass in the case of an antifoaming agent, In the case of a metal deactivator, 0.005 to 1% by mass is preferable, and in the case of other additives, 0.1 to 15% by mass is preferable.
本潤滑油組成物の粘度は特に制限されないが、４０℃における動粘度の範囲は、好ましくは６８０ｍｍ２／ｓ以下、より好ましくは２２０ｍｍ２／ｓ以下であり、また、好ましくは２ｍｍ２／ｓ以上、より好ましくは８ｍｍ２／ｓ以上である。
１００℃における動粘度の範囲は、好ましくは２５ｍｍ２／ｓ以下、より好ましくは２０ｍｍ２／ｓ以下、更に好ましくは１５ｍｍ２／ｓ以下、特に好ましくは１０ｍｍ２／ｓ以下であり、また、好ましくは１．０ｍｍ２／ｓ以上、より好ましくは１．５ｍｍ２／ｓ以上、更に好ましくは２ｍｍ２／ｓ以上、特に好ましくは２．５ｍｍ２／ｓ以上である。また、上記基油の粘度指数は特に制限されないが、好ましくは８５以上、より好ましくは１００以上、更に好ましくは１２０以上である。
The viscosity of the lubricating oil composition is not particularly limited, but the range of kinematic viscosity at 40 ° C. is preferably 680 mm 2 / s or less, more preferably 220 mm 2 / s or less, and preferably 2 mm 2 / s or more. More preferably, it is 8 mm 2 / s or more.
Range of kinematic viscosity at 100 ° C. is preferably not more than 25 mm 2 / s, more preferably 20 mm 2 / s or less, more preferably 15 mm 2 / s or less, particularly preferably not more than 10 mm 2 / s, also preferably It is 1.0 mm 2 / s or more, more preferably 1.5 mm 2 / s or more, further preferably 2 mm 2 / s or more, and particularly preferably 2.5 mm 2 / s or more. The viscosity index of the base oil is not particularly limited, but is preferably 85 or more, more preferably 100 or more, and still more preferably 120 or more.
また、本発明の潤滑油組成物においては、熱・酸化安定性を高めて特にスラッジ生成量を十分に低減する点から、当該組成物中の硫黄含有量（元素換算値）が、組成物全量基準で、０．０２質量％以下であることが好ましく、０．０１５質量％以下であることがより好ましく、０．０１質量％以下であることが更に好ましい。ここでいう硫黄含有量とは、ＪＩＳ Ｋ２５４１「原油及び石油製品−硫黄分試験方法」の「微量電量滴定式酸化法」により測定される値をいう。 In addition, in the lubricating oil composition of the present invention, the sulfur content (element-converted value) in the composition is the total amount of the composition from the viewpoint of enhancing the heat and oxidation stability and particularly reducing the sludge generation amount sufficiently. On the basis, it is preferably 0.02% by mass or less, more preferably 0.015% by mass or less, and further preferably 0.01% by mass or less. The sulfur content here refers to a value measured by “microcoulometric titration method” of JIS K2541 “Crude oil and petroleum products—Sulfur content test method”.
本発明の潤滑油組成物は、圧縮機及び増速歯車装置を備えるタービン装置の潤滑油として好ましく使用される。タービン装置には、水力タービン、蒸気タービン、ガスタービン等があるが、本発明の潤滑油組成物は特にガスタービン装置に用いた場合に優れた効果を発揮する。このようなガスタービン装置の出力数に特に制限はない。 The lubricating oil composition of the present invention is preferably used as a lubricating oil for a turbine apparatus including a compressor and a speed increasing gear device. Turbine devices include hydraulic turbines, steam turbines, gas turbines, and the like. The lubricating oil composition of the present invention exhibits excellent effects particularly when used in gas turbine devices. There is no restriction | limiting in particular in the output number of such a gas turbine apparatus.
また、本発明の潤滑油組成物は、その優れた特性から、上記用途の他、油圧作動油、工業用ギヤ油、軸受油、圧縮機油等の用途においても好ましく使用することができる。 Moreover, the lubricating oil composition of the present invention can be preferably used in applications such as hydraulic fluids, industrial gear oils, bearing oils, compressor oils, etc., in addition to the above applications, due to its excellent characteristics.
以下、実施例及び比較例に基づき本発明を更に具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
［実施例１〜２、比較例１〜８］
実施例１〜２及び比較例１〜６の調製に当り、以下の基油及び添加剤を用意した。
基油１：ＸＨＶＩ５．２（登録商標）
フィッシャートロプッシュ法により合成されたＧＴＬ基油で、ＡＰＩ（米国石油
協会）基油分類によりグループ３に分類されるもの。（特性：１００℃における動
粘度；５．１０ｍｍ２／ｓ、４０℃における動粘度；２３．５ｍｍ２／ｓ、粘度指
数；１５３、１５℃密度；０．８２１、硫黄分含有量（硫黄元素換算値）；１０
ｐｐｍ未満、窒素分含有量（窒素元素換算値）；１ｐｐｍ未満、ＡＳＴＭ Ｄ３２
３８法による環分析のアロマ分；１％未満）
基油２：ＧｒII
原油を常圧蒸留して得られた潤滑油留分に対して、水素化分解、溶剤脱ろうなど
の精製手段を適宜組み合わせて適用することにより得られたパラフィン系鉱油
（特性：１００℃における動粘度；１０．９ｍｍ２／ｓ、４０℃における動粘度；
９１．２ｍｍ２／ｓ、粘度指数；１０４、硫黄分含有量（硫黄元素換算値）；１０
ｐｐｍ未満）
[Examples 1-2, Comparative Examples 1-8]
In the preparation of Examples 1-2 and Comparative Examples 1-6, the following base oils and additives were prepared.
Base oil 1: XHVI5.2 (registered trademark)
GTL base oil synthesized by the Fischer-Tropsch method and classified as Group 3 by API (American Petroleum Institute) base oil classification. (Characteristics:; kinematic viscosity at 5.10mm 2 / s, 40 ℃; kinematic viscosity at 100 ℃ 23.5mm 2 / s, viscosity number finger; 153,15 ° C. Density; 0.821, sulfur content (elemental sulfur Conversion value); 10
Less than ppm, nitrogen content (nitrogen element equivalent); less than 1 ppm, ASTM D32
(Aroma content of ring analysis by 38 method; less than 1%)
Base oil 2: GrII
Paraffinic mineral oil obtained by applying a suitable combination of hydrocracking, solvent dewaxing and other refining means to a lubricating oil fraction obtained by atmospheric distillation of crude oil (Characteristics: Dynamics at 100 ° C) Viscosity: 10.9 mm 2 / s, kinematic viscosity at 40 ° C .;
91.2 mm 2 / s, viscosity index; 104, sulfur content (sulfur element equivalent value); 10
(below ppm)
添加剤Ａ１：テトラプロペニルコハク酸、及びその１，３−プロパンジオールとのエステ
ル化合物の混合物（ＪＩＳ
Ｋ２５０１による酸価１６５ｍｇＫＯＨ／ｇ）
添加剤Ａ２：オレイルザルコシン酸（グリシンの誘導体）
添加剤Ｂ１：β−ジチオホスホリル化プロピオン酸
添加剤Ｂ２：トリス（ｉｓｏ−プロピルフェニル）ホスフェート
添加剤Ｃ１：アルキル化フェニルナフチルアミン
添加剤Ｃ２：オクチル化・ブチル化ジフェニルアミン
添加剤Ｃ３：トリス（ジｔ−ブチルフェニル）フォスファイト
添加剤Ｄ ：ベンゾトリアゾール
添加剤Ｅ ：アルキルポリアルコキシエステル
Additive A1: Tetrapropenyl succinic acid and its mixture of ester compounds with 1,3-propanediol (JIS
Acid value according to K2501 165 mgKOH / g)
Additive A2: Oleyl sarcosine acid (derivative of glycine)
Additive B1: β-dithiophosphorylated propionic acid additive B2: tris (iso-propylphenyl) phosphate additive C1: alkylated phenylnaphthylamine additive C2: octylated / butylated diphenylamine additive C3: tris (di-t- Butylphenyl) phosphite additive D: Benzotriazole additive E: Alkyl polyalkoxy ester
上記基油及び添加剤を用いて、表１〜４に示す組成を有する実施例１〜２、比較例１〜６の潤滑油組成物を調製し、また、比較例７、８の市販ガスタービン油を用意した。 Using the above base oil and additives, the lubricating oil compositions of Examples 1-2 and Comparative Examples 1-6 having the compositions shown in Tables 1-4 were prepared, and the commercial gas turbines of Comparative Examples 7 and 8 were prepared. Oil was prepared.
（粘度等の測定）
上記実施例１〜２、比較例１〜８の各潤滑油組成物について、４０℃の動粘度（ＪＩＳ
Ｋ２２８３に基づく）、１００℃の動粘度（ＪＩＳ Ｋ２２８３に基づく）、粘度指数（ＪＩＳ Ｋ２２８３に基づく）、及び酸価（ＪＩＳ Ｋ２５０１に基づく）を測定した。
各測定結果を表１〜表４に示す。
(Measurement of viscosity, etc.)
About each lubricating oil composition of the said Examples 1-2 and Comparative Examples 1-8, 40 degreeC kinematic viscosity (JIS)
(Based on K2283), kinematic viscosity at 100 ° C. (based on JIS K2283), viscosity index (based on JIS K2283), and acid value (based on JIS K2501).
Each measurement result is shown in Tables 1 to 4.
（試験）
実施例１〜２及び比較例１〜８の各潤滑油組成物を用いて、その性能を見るために以下の試験を行った。
(test)
Using the lubricating oil compositions of Examples 1 and 2 and Comparative Examples 1 to 8, the following tests were performed to see the performance.
（錆止め性試験）
ＪＩＳ Ｋ２５１０に基づき、恒温槽内に設置した容器に、試料油３００ｍｌを採取し、毎分１０００回転で攪拌する。６０℃になったときに、鉄製試験片を試料油中に挿入し、更に人工海水を３０ｍｌ加え、６０℃に保ったまま２４時間攪拌を続け、その後試験片を取り出し、試験片のさびの発生状態を目視で評価する。
評価基準：さびなし；錆の発生が見られない（０％）
軽 微；１ｍｍ以下の点さび６個以下
中 度；上記軽微を超え、表面積の５％未満
高 度；上記中度を超え、表面積の５％以上
(Rust prevention test)
Based on JIS K2510, 300 ml of sample oil is collected in a container installed in a thermostat and stirred at 1000 revolutions per minute. When the temperature reaches 60 ° C., insert an iron test piece into the sample oil, add 30 ml of artificial seawater, continue stirring for 24 hours while maintaining the temperature at 60 ° C., and then remove the test piece to generate rust on the test piece. The condition is evaluated visually.
Evaluation criteria: No rust; no occurrence of rust (0%)
Minor: Less than 6 point rust of 1mm or less
Medium; above minor and less than 5% of surface area
Altitude: Above the above medium, 5% or more of the surface area
（極圧性試験）
ＡＳＴＭ Ｄ ５１８２−９１で標準化された試験方法により、ＦＺＧ歯車潤滑性能試験を行い、各潤滑油組成物の極圧性を評価した。ＦＺＧ歯車試験において不合格となった荷重ステージを潤滑性能評価の指標とした。
(Extreme pressure test)
The FZG gear lubrication performance test was conducted by a test method standardized by ASTM D 5182-91, and the extreme pressure properties of each lubricating oil composition were evaluated. The load stage that failed in the FZG gear test was used as an index for evaluating the lubricating performance.
（熱・酸化安定性試験：Ｄｒｙ ＴＯＳＴ試験）
ＪＩＳ Ｋ ２５１４のＴＯＳＴ（タービン油酸化安定度試験）に規定する試験において、純水を加えずに試験油量を３６０ｍｌとし、オイルバスで１２０℃に加熱し、その温度に保持しながら３Ｌ／ｈの流量で酸素を吹き込んだ。触媒にはコイル状銅及び鉄触媒を用いた。酸素の吹き込み開始時刻から起算して５００時間後に、試験油を室温まで冷却させた後、酸化劣化した潤滑油組成物の全量を孔径１．０μｍのメンブランフィルターで濾過し、フィルター上の不溶分を秤量し、試験油量１００ｍｌ当りの不溶分のｍｇ数、すなわちｍｇ／１００ｍｌでスラッジ量を測定した。
(Thermal and oxidation stability test: Dry TOST test)
In the test specified in TOST (turbine oil oxidation stability test) of JIS K 2514, the amount of test oil is 360 ml without adding pure water, heated to 120 ° C. in an oil bath, and kept at that temperature, 3 L / h Oxygen was blown at a flow rate of. Coiled copper and iron catalysts were used as the catalyst. After 500 hours from the oxygen blowing start time, the test oil was cooled to room temperature, and then the entire amount of the oxidatively deteriorated lubricating oil composition was filtered through a membrane filter having a pore size of 1.0 μm to remove insoluble matter on the filter. The amount of sludge was measured by measuring the number of mg of insoluble matter per 100 ml of test oil, that is, mg / 100 ml.
（ＲＰＶＯＴ試験）
上記のＤｒｙ ＴＯＳＴ試験を終えたろ過油の酸化寿命を、同ＪＩＳ規格試験のＲＰＶＯＴで標準化された方法にて測定した。予め測定しておいた新油のＲＰＶＯＴ値で酸化試験時後の酸化劣化油のＲＰＶＯＴ値を除し、ＲＰＶＯＴ残存率とした。
酸化劣化油のＲＰＶＯＴ値が大きく、また、ＲＰＶＯＴ残存率に対する不溶分量が少ないほど熱・酸化安定性が良好であることを意味する。
(RPVOT test)
The oxidation life of the filtered oil after the Dry TOST test was measured by a method standardized by RPVOT of the JIS standard test. The RPVOT value of the oxidatively deteriorated oil after the oxidation test was divided by the RPVOT value of the new oil measured in advance to obtain the RPVOT residual rate.
It means that heat / oxidation stability is so favorable that the RPVOT value of oxidation degradation oil is large, and the amount of insoluble matter with respect to the RPVOT residual rate is small.
（試験結果）
各試験結果を表１〜４に示す。
比較例１〜４については、錆止め性試験において、その評価基準で軽微〜高度の錆が発生しており、タービン油として使用することができないことが判った。従って、ＦＺＧ歯車試験及びＤｒｙ ＴＯＳＴ試験は行わなかった。
また、比較例５〜６については、錆止め性試験において、錆の発生が見られなかったが、ＦＺＧ歯車試験における結果は、比較例５が８ＦＬＳ、比較例６が７ＦＬＳであって、タービン油とギヤ油の兼用油としての要求基準９ＦＬＳ以上を満たしておらず、タービン油とギヤ油の兼用油としての使用に適さないことが判った。従って、Ｄｒｙ ＴＯＳＴ試験は行わなかった。
(Test results)
Each test result is shown in Tables 1-4.
About Comparative Examples 1-4, in the rust prevention property test, it turned out that slight-high degree rust has generate | occur | produced by the evaluation criteria, and cannot be used as turbine oil. Therefore, the FZG gear test and the Dry TOST test were not performed.
Moreover, about Comparative Examples 5-6, although generation | occurrence | production of rust was not seen in the rust prevention property test, the result in the FZG gear test is 8 FLS in Comparative Example 5 and 7 FLS in Comparative Example 6, and the turbine oil and It has been found that it does not meet the requirement standard 9FLS or more for combined use of gear oil and is not suitable for use as combined oil of turbine oil and gear oil. Therefore, the Dry TOST test was not performed.
（評価）
表１に示した結果から明らかなように、実施例１、２のコハク酸及び／又はそのエステルとグリシンの誘導体を併用した潤滑油組成物は、いずれも錆止め性試験において、錆の発生が見られず高い防錆性を示していることが判る。また、ＦＺＧ歯車試験における結果も１１ＦＬＳ（実施例１）、１０ＦＬＳ（実施例２）と良好で優れた極圧性を示し、Ｄｒｙ ＴＯＳＴ試験におけるスラッジ量も２．９ｍｇ／１００ｍｌ（実施例１）、１．９ｍｇ／１００ｍｌ（実施例２）と少なく耐スラッジ性、及び十分に長い酸化寿命を有していることが確認され、実施例１、２はタービン油とギヤ油の兼用油としても好適なことが判った。
表２〜表４に示すように、比較例１〜６のものは、コハク酸及び／又はそのエステルまたはグリシンの誘導体の一方を使用したものであり、上記したように、錆止め性試験において、その評価基準で軽微〜高度の錆が発生しているか（比較例１〜４）、錆の発生が見られなくてもＦＺＧ歯車試験における結果が８ＦＬＳ、７ＦＬＳと小さく（比較例５，６）、タービン油とギヤ油の兼用油として使用するには不適格である。
また、比較例７の市販ガスタービン油Ａは、錆止め性試験において錆の発生が見られず、ＦＺＧ歯車試験においても１２ＦＬＳと良好な結果が出ているが、Ｄｒｙ ＴＯＳＴ試験においてスラッジ量が７３ｍｇ／１００ｍｌと非常に多いし、比較例８の市販ガスタービン油Ｂでは、錆止め性試験において錆の発生が見られず、スラッジ量も比較的少ないが、ＦＺＧ歯車試験における結果が８ＦＬＳと低く、いずれも満足の行くものとは言えない。
(Evaluation)
As is clear from the results shown in Table 1, all of the lubricating oil compositions using the succinic acid and / or ester thereof in Examples 1 and 2 and a derivative of glycine showed the occurrence of rust in the rust prevention test. It turns out that it shows high rust prevention. Further, the results in the FZG gear test also showed excellent and excellent extreme pressure properties of 11 FLS (Example 1) and 10 FLS (Example 2), and the amount of sludge in the Dry TOST test was 2.9 mg / 100 ml (Example 1), 1 .9 mg / 100 ml (Example 2), it is confirmed that it has a low sludge resistance and a sufficiently long oxidation life, and Examples 1 and 2 are also suitable as a combined oil for turbine oil and gear oil. I understood.
As shown in Tables 2 to 4, Comparative Examples 1 to 6 are ones using one of succinic acid and / or its ester or glycine derivative , and as described above, in the rust prevention test, Whether light to high rust is generated according to the evaluation criteria (Comparative Examples 1 to 4), or the result in the FZG gear test is as small as 8FLS and 7FLS (Comparative Examples 5 and 6) It is not suitable for use as a combination oil and gear oil.
Further, in the commercial gas turbine oil A of Comparative Example 7, no rust was observed in the rust prevention test, and an excellent result of 12 FLS was obtained in the FZG gear test, but the amount of sludge in the Dry TOST test was 73 mg / kg. The commercial gas turbine oil B of Comparative Example 8 has a very large amount of 100 ml, and no rust is generated in the rust prevention test and the amount of sludge is relatively small, but the result in the FZG gear test is as low as 8 FLS. It cannot be said to be satisfactory.
Claims (9)
（ｂ）下記式１に示すコハク酸及び／又は炭素数１〜３０のアルコールとの部分エステルを０．０４〜０．１質量％、
（ｃ）下記式２に示すグリシンの誘導体を０．００５〜０．０１質量％、
（ｄ）少なくとも１種以上のリン化合物を含むリン系極圧剤、並びに
（ｅ）芳香族アミン化合物、
を含有することを特徴とする圧縮機及び増速歯車装置を備えるタービン装置用潤滑油組成物。 (A) at least one base oil selected from mineral oil and synthetic oil,
(B) 0.04 to 0.1% by mass of a partial ester with succinic acid and / or an alcohol having 1 to 30 carbon atoms represented by the following formula 1 .
(C) 0.005 to 0.01% by mass of a glycine derivative represented by the following formula 2;
( D) a phosphorus-based extreme pressure agent containing at least one phosphorus compound, and
(E) an aromatic amine compound,
A lubricating oil composition for a turbine device comprising a compressor and a speed increasing gear device, comprising:
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