CN105802697B - A kind of preparation method of the degradable methanol engine lubricating oil of improved plant oil base - Google Patents
A kind of preparation method of the degradable methanol engine lubricating oil of improved plant oil base Download PDFInfo
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- CN105802697B CN105802697B CN201610176094.7A CN201610176094A CN105802697B CN 105802697 B CN105802697 B CN 105802697B CN 201610176094 A CN201610176094 A CN 201610176094A CN 105802697 B CN105802697 B CN 105802697B
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- oil
- parts
- preparation
- degradable
- lubricating oil
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010773 plant oil Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003921 oil Substances 0.000 claims abstract description 48
- 235000019198 oils Nutrition 0.000 claims abstract description 48
- -1 heating Chemical compound 0.000 claims abstract description 43
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 28
- 239000003549 soybean oil Substances 0.000 claims abstract description 28
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 25
- 239000008158 vegetable oil Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012153 distilled water Substances 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 239000002585 base Substances 0.000 claims abstract description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 239000003599 detergent Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000007866 anti-wear additive Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 235000019253 formic acid Nutrition 0.000 claims abstract description 8
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 7
- FMIMFCRXYXVFTA-FUAOEXFOSA-N (4as,6ar,6as,6br,8ar,12ar,14bs)-2,2,6a,6b,9,9,12a-heptamethyl-10-oxo-3,4,5,6,6a,7,8,8a,11,12,13,14b-dodecahydro-1h-picene-4a-carboxylic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CCC(C)(C)C[C@H]5C4=CC[C@@H]3[C@]21C FMIMFCRXYXVFTA-FUAOEXFOSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 11
- FMIMFCRXYXVFTA-UHFFFAOYSA-N 3-Oxo-12-oleanen-28-oic acid Natural products C1CC(=O)C(C)(C)C2CCC3(C)C4(C)CCC5(C(O)=O)CCC(C)(C)CC5C4=CCC3C21C FMIMFCRXYXVFTA-UHFFFAOYSA-N 0.000 claims description 10
- FFDHYUFECJTEAY-UHFFFAOYSA-N epimacherinic acid Natural products CC1(C)CCC2(CCC3(C)C(CCC4C5(C)CCCC(C)(C)C5CCC34C)C2C1)C(=O)O FFDHYUFECJTEAY-UHFFFAOYSA-N 0.000 claims description 10
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000013517 stratification Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 238000005341 cation exchange Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000013556 antirust agent Substances 0.000 abstract description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003729 cation exchange resin Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- 239000002518 antifoaming agent Substances 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
- 239000000446 fuel Substances 0.000 description 7
- 150000003900 succinic acid esters Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- PYNAWELXQDNXOD-UHFFFAOYSA-N n-hexyl-n-phenylaniline Chemical class C=1C=CC=CC=1N(CCCCCC)C1=CC=CC=C1 PYNAWELXQDNXOD-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 229920001577 copolymer Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000010721 machine oil Substances 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
- 239000000047 product Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000158728 Meliaceae Species 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 2
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 2
- 150000005002 naphthylamines Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- DDQBQEISPISFNY-UHFFFAOYSA-N C(CCCCCCC)OS(=O)(=O)C1=NC=NC(=N1)S(=O)(=O)OCCCCCCCC Chemical class C(CCCCCCC)OS(=O)(=O)C1=NC=NC(=N1)S(=O)(=O)OCCCCCCCC DDQBQEISPISFNY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000002283 diesel fuel Substances 0.000 description 1
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- 229940035422 diphenylamine Drugs 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- XUMOVISJJBHALN-UHFFFAOYSA-N n-butyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCC)C1=CC=CC=C1 XUMOVISJJBHALN-UHFFFAOYSA-N 0.000 description 1
- VCQJSMBSGMLFKI-UHFFFAOYSA-N n-heptyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCC)C1=CC=CC=C1 VCQJSMBSGMLFKI-UHFFFAOYSA-N 0.000 description 1
- MKEUPRYKXJEVEJ-UHFFFAOYSA-N n-hexyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCC)C1=CC=CC=C1 MKEUPRYKXJEVEJ-UHFFFAOYSA-N 0.000 description 1
- ZLNMGXQGGUZIJL-UHFFFAOYSA-N n-octyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCCC)C1=CC=CC=C1 ZLNMGXQGGUZIJL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/04—Fatty oil fractions
-
- 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
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- 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
- C10M2207/283—Esters of polyhydroxy compounds
-
- 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
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to a kind of preparation methods of the degradable methanol engine lubricating oil of improved plant oil base, belong to technical field of lubricating oil.Step: taking soybean oil, adds acid cation exchange resin, heating, hydrogen peroxide is added dropwise, formic acid is reacted, after reaction, it is washed, separates water layer, the distilled water of the modified soybean oil heat on upper layer is washed, water phase is discarded, then is neutralized with alkali, then is washed to pH neutrality with distilled water, after vacuum distillation removes moisture, modified vegetable oil is obtained；Modified vegetable oil, polyol ester, antioxidant, antirust agent, extreme pressure anti-wear additives and ashless system's detergent dispersant are uniformly mixed, heated, it is cooling, obtain lubricant oil composite.The lubricating oil that the present invention is prepared is suitable for methanol engine, and greasy property is good, biodegradable.
Description
Technical field
The present invention relates to a kind of preparation methods of the degradable methanol engine lubricating oil of improved plant oil base, belong to lubrication
Oil tech field.
Background technique
In automobilism engine motor oil consumption costs and less but it but influence automobile dynamic property, economy more
It is important that therefore functional reliability and service life that it influences engine make according to the performance of engine, structure and combination
Correctly select machine oil particularly significant with condition.The effect of engine lubrication mainly includes: 1, lubricating action: engine operation
Shi Ruguo, which cannot suitably lubricate the parts to run at high speed, will occur caused by metal and intermetallic dry friction friction
Heat can make the metal molten of rubbing surface make the stuck and good profit essence of parts that can make machine oil engaging friction machine within a very short time
Being adhered to friction surface forming layer oil film between part and being not directly contacted with two rubbing surfaces as far as possible becomes intermetallic dry friction
Fluid friction between liquid oil layer；2, cooling effect: maximum combustion temperature may be up to 2400 DEG C when engine operation, even if
The mean temperature of idling speed lower combustion chamber also at 1000 DEG C or more, the part contacted with high-temperature fuel gas by heat intensive at this time
It must carry out to which but otherwise to be stranded temperature excessively high and burn out for engine；3, anti-rust action: engine atmosphere in work or storage
Water and the sour gas that generates of when burning can generate corrosiveness machine oil to parts and can be adsorbed on metal surface and prevent sour gas
Body and water are to corrosion of metal.
It is constantly progressive, the demand of the energy is increasingly increased, energy problem is at restriction economic development with industrialized
Big factors therefore substitute the research and use of the substitute fuel of petroleum, grown rapidly, currently, technically more
Molding substitute fuel has: methanol, the substitute fuel that ethyl alcohol is gasoline；(such as: China's most area promotes 10% ethanol vapor
Oil) dimethyl ether, the alternative fuel that monoesters is diesel oil；It can be seen that alcohol ethers have become mainstream, alcohol ethers as alternative fuel
As alternative fuel, although playing certain effect to energy shortages is alleviated, certain technical problems in popularization are answered
Cause enough attention.Especially alcohol ether class A fuel A is in use to the important additives in engine lubricating oil composition
The decomposition of ZDDP (zinc dialkyl dithiophosphate), has seriously affected the antioxygenic property of former engine lubricating oil, has made it
Oil draining period greatly shortens, and engine intake valve carbon distribution generates tendency and greatly increases, and long-term accumulated can seriously affect making for engine
Use performance.
CN103897775A discloses a kind of different proportion alcohol engine oil ageing inhibitor and its preparation side
Method.The present invention dredges base thiadiazoles 3~35% by N- phenyl-α naphthylamine 5~45%, 2,5-, amido borate 10~60%, is modified
One group of compound additive that low alkali value calcium mahogany sulfonate 15~40%, flux oil 5~10% form.Preparation method of the invention
It is: by 55~65 DEG C so far of flux oil heating, is then successively separately added into N- phenyl-α naphthylamine, 2,5- dredges base thiadiazoles, amido
45~50 DEG C of borate, modified low alkali value calcium mahogany sulfonate constant temperature stirrings are no less than 45min.CN105176637A discloses one kind
Biology base methanol gasoline engine specific complex lubricating oil and preparation method thereof.The present invention is that squeeze into base oil can heating stirring
Reaction kettle device in, be heated up to 75 DEG C, constant temperature stirs 1 hour；Then viscosity modified component is added, is heated up to 80 DEG C, constant temperature
Stirring 30 minutes；By obtained mixture temperature drop to 75 DEG C, antioxygen antirust component, the anti-glue component of antioxygen, auxiliary antioxygen group is added
Divide, metal detergent component, ashless dispersants component, extreme-pressure anti-wear component, metal anti-attrition component, anti-cream demulsification component, pour point depression component
And oily components stir 20 minutes at 75 DEG C；Then anti-bubble component is added to stir 30 minutes；Finally obtained mixture is used
Cutter do it is pre- shearing 1 hour after filtering, detection, settled in settling tank 24 hours to get.
But the cost of material of above-mentioned lubricating oil is high, and still has abrasion resistance when use in Alcohol engines
Bad problem；And above-mentioned engine lubricating oil cannot be preferably biodegradable, will affect environment.
Summary of the invention
The object of the present invention is to provide a kind of lubricating oil applied to methanol engine, which needs to have preferable
Biodegradable, which is that oil is prepared based on epoxy-modified vegetable oil.
Technical solution is as follows:
A kind of preparation method of the degradable methanol engine lubricating oil of improved plant oil base, comprises the following steps that
The preparation of modified vegetable oil: step 1 by weight, takes 100~120 parts of soybean oil, adds acid cation
1~3 part of exchanger resin, heating, be slowly added dropwise 5~10 parts of hydrogen peroxide, 3~6 parts of formic acid reacted, after reaction, carry out
Washing, separates water layer, and the distilled water of the modified soybean oil heat on upper layer is washed, and discards water phase, then neutralized with alkali, then
PH neutrality, which is washed to, with distilled water obtains modified vegetable oil after vacuum distillation removes moisture；
Step 2, by weight, by 30~40 parts of polyalcohol, 20~30 parts of ethanedioic acid, 20~30 parts of oleanonic acid,
3~5 parts of catalyst, 80~120 parts of organic solvent be uniformly mixed, then heat up, reacted, steam organic solvent, obtain more
First alcohol ester；
Step 3, by weight, by 70~80 parts of modified vegetable oil, 5~10 parts of polyol ester, antioxidant 0.05~1
Part, 0.05~1 part of antirust agent, 0.05~1 part of extreme pressure anti-wear additives and 0.05~1 part of ashless system's detergent dispersant are uniformly mixed, and are added
Heat is cooling to 70~120 DEG C, obtains lubricant oil composite.
In the step 1, heating is to make temperature to 50~60 DEG C, and the reaction time is that carry out 1~3 after being added dropwise again small
When.In the step 1,50~60 DEG C of temperature of the distilled water of the heat.
In the step 2, the polyalcohol in hydroxymethyl-propane, glycerine, pentaerythrite, mannitol one
Kind or several mixing.
Reaction time in the step 2 is 2~4 hours, 70~90 DEG C of reaction temperature.
The extreme pressure anti-wear additives are phosphate compounds, phosphite ester compound, sulphur phosphorus complexing agent or sulfur-bearing pole
Press agent.
In the step 1, soybean oil is needed by pretreatment, and the preprocess method is as follows: taking 200mL soybean
When temperature rises to 35 DEG C the ammonium hydroxide of the about 4wt% of oil volume a quarter is added, after adding in oil, heating in 20min
Continue to stir 15min, then stop stirring, be warming up to 95 DEG C, keeps 1h；Reaction mixture is poured into separatory funnel, is stood
Layering separates and rinses oil reservoir with boiling water after soap stock water；The oil reservoir separated is warming up to 93~97 DEG C again, in 10 minutes thereto
The H of the 30wt% of oil volume 5% is added2O2, stop stirring, keep the temperature 1h at 120 DEG C；Stratification separates soap stock with separatory funnel
Water；Oil reservoir, then stratification are rinsed with boiling water, water layer is removed, obtains pretreated soybean oil.
Beneficial effect
The lubricating oil that the present invention is prepared is suitable for methanol engine, and greasy property is good, biodegradable.
Specific embodiment
In the lubricant oil composite that the present invention uses, by the way that its biodegrade can be improved to soybean oil progress is epoxy-modified
Speed, while can also improve greasy property.Polyol ester is basic components, and oleanonic acid, which is added, in preparation step to mention
High biological degradability.
In addition, organic solvent is not particularly limited in ester rouge reaction process, hexane, hexamethylene, heptane etc. can be enumerated
The alcohols such as the arene compounds such as alkanes, toluene, dimethylbenzene, methanol, ethyl alcohol, isopropanol, butanol, hexanol, cyclohexanol.Separately
Outside, the ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cycloheptanone, cyclohexanone, ether, tetrahydrofuran, two according to circumstances also can be used
Nitrile compounds such as the ester compounds such as the ethers such as oxinane, ethyl acetate, butyl acetate, methyl formate, acetonitrile etc..
It in the lubricant oil composite being prepared, is not damaging within the scope of the object of the invention, can be added as needed each
Kind additive, such as: ashless system's detergent dispersant, antioxidant, antirust agent, metal deactivator, viscosity index improver, flow point
At least one selected in depressant and defoaming agent etc..
Herein, ashless system's detergent dispersant can be enumerated, such as: succinimide class, boracic succinimide class, benzylamine
Unitary or dicarboxylic acids amides etc. representated by class, boracic benzylamine class, succinic acid esters, fatty acid or succinic acid.It is ashless
It is the combined amount of detergent dispersant, considers from the balance of effect and economy, on the basis of the total amount of composition,
The left and right 0.01wt% or more, 5wt% or less.
As antioxidant, can be used amine antioxidant used in existing lubricating oil, phenolic antioxidant and
Sulfur antioxidant.These antioxidants can be used alone or combine two or more use.It is arranged as amine antioxidant
It lifts, such as: the monoalkyls hexichol amine compound such as single octyl diphenylamine, single nonyl diphenylamine；4,4 '-dibutyl diphenylamines, 4,
4 '-diamyl diphenylamines, 4,4 '-dihexyl diphenylamines, 4,4 '-diheptyl diphenylamines, 4,4 '-dioctyl diphenylamines, 4,4 '-two
The dialkyl diphenylamines based compound such as nonyl diphenylamine；Tetrabutyl diphenylamines, four hexyl diphenylamines, four octyl diphenylamines, four nonyls
The poly- alkyl diphenyl amine compound such as base diphenylamines；Alpha-naphthylamine, phenyl-α-naphthylamine, butyl phenyl-alpha-naphthylamine, benzyl phenyl-α-
The naphthylamines systems such as naphthylamines, hexyl phenyl-α-naphthylamine, heptyl phenyl-α-naphthylamine, octyl phenyl-alpha-naphthylamine, nonyl phenyl-α-naphthylamine
Compound.Phenolic antioxidant can be enumerated, such as: 2,6- di-t-butyl -4- aminomethyl phenyls, 2,6- di-t-butyl -4- ethylo benzene
The monophenols based compounds, 4 such as base, octadecyl -3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic ester, 4 '-di-2-ethylhexylphosphine oxides-(2,
6- DI-tert-butylphenol compounds), the hexichol phenol system compound such as 2,2 '-di-2-ethylhexylphosphine oxides-(4- ethyl -6- tert-butyl phenol).
Sulfur antioxidant can be enumerated, such as 2,6- di-t-butyl -4- (4,6- bis- (octylsulfo) -1,3,5-triazines -2-
Base amino) the thio terpene hydro carbons based compound such as reactant of phenol, phosphoric sulfide and firpene, two laruyl alcohol thiodipropionates,
Dialkyls dipropionates such as distearyl alcohol thiodipropionate etc..
Antirust agent can enumerate metal system sulfonate, alkenyl succinic acid ester etc..The combined amount of these antirust agent is imitated from mixing
From the aspect of fruit, on the basis of total composition, about in 0.01wt% or more, 0.5wt% or less.
As metal deactivator (copper anticorrosive), can enumerate, such as: enumerate BTA system, tolyl-triazole system, thiophene two
Azoles system, imidazoles system and pyrimidine compound etc..Wherein, preferred benzotriazole based compound.The combined amount of these metal deactivators,
From the aspect of mixed effect, on the basis of total composition, about in 0.01wt% or more, 0.1wt% or less.
As viscosity index improver, can enumerate, such as: polymethacrylates, distributed polymethacrylates,
Olefin copolymer (e.g., ethylene-propylene copolymer etc.), distributed olefin copolymer, styrene based copolymer (such as benzene second
Alkene-diene copolymers, styrene-isoprene copolymer etc.) etc..The combined amount of these viscosity index improvers is imitated from mixing
From the aspect of fruit, on the basis of total composition, about in 0.5wt% or more, 15wt% or less.
Flow point depressant can be enumerated: ethylene-vinyl acetate copolymer, the condensation product of chlorinated paraffin and naphthalene, chlorinated paraffin
With the condensation product, polymethacrylates, alkyl styrenes of phenol etc., for instance, it may be preferable to using matter average molecular weight 50,000 with
Above, 150,000 or less Zuo You polymethacrylates.The combined amount of flow point depressant is about existed on the basis of total composition
0.1wt% or more, 5wt% or less.
The preferred polymeric silicone system defoaming agent of defoaming agent, polyacrylate system defoaming agent, by mixing the polymeric silicone
It is that defoaming agent etc. can effectively play defoaming.Such polymeric silicone system defoaming agent can enumerate for example organic poly- silicon oxygen
Alkane is especially suitable for the fluorine-containing organopolysiloxanes such as three fluoro hydroxypropyl methyl silicone oil.The combined amount of defoaming agent, from defoaming effect with
And the balance of economy considers, on the basis of the total amount of composition, about in 0.005wt% or more, 0.1wt% or less.
Biodegradable lubricant composition of the invention, because lubricity, oxidation stability and biological degradability are excellent
It is different, so can suitably be applied to the use in such as methanol engine.
For the soybean oil used in following embodiment by pretreatment, the preprocess method is as follows: taking 200mL soybean
When temperature rises to 35 DEG C the ammonium hydroxide of the about 4wt% of oil volume a quarter is added, after adding in oil, heating in 20min
Continue to stir 15min, then stop stirring, be warming up to 95 DEG C, keeps 1h；Reaction mixture is poured into separatory funnel, is stood
Layering separates and rinses oil reservoir with boiling water after soap stock water；The oil reservoir separated is warming up to 93~97 DEG C again, in 10 minutes thereto
The H of the 30wt% of oil volume 5% is added2O2, stop stirring, keep the temperature 1h at 120 DEG C；Stratification separates soap stock with separatory funnel
Water；Oil reservoir, then stratification are rinsed with boiling water, water layer is removed, obtains pretreated soybean oil.
Catalyst used in step 2 esterification is solid super acid catalyst SO in following embodiment4 2-/ZrO2。
Embodiment 1
Step 1, the preparation of modified vegetable oil: by weight, taking 100 parts of soybean oil, adds acid cation exchange
1 part of resin, be warming up to 50 DEG C, be slowly added dropwise 5 parts of hydrogen peroxide, 3 parts of formic acid reacted, the reaction time be after being added dropwise again into
It row 1 hour, after reaction, is washed, separates water layer, the modified soybean oil on upper layer carries out water with 50 DEG C of hot distilled water
It washes, discards water phase, then neutralized with alkali, then be washed to pH neutrality with distilled water and be modified after vacuum distillation removes moisture
Vegetable oil；
Step 2, by weight, by 30 parts of pentaerythrite, 20 parts of ethanedioic acid, 20 parts of oleanonic acid, catalyst 3~5
Part, 80 parts of organic solvent be uniformly mixed, then heat up, reacted, the reaction time is 2 hours, 70 DEG C of reaction temperature, has been steamed
Solvent obtains polyol ester；
Step 3, by weight, by 70 parts of modified vegetable oil, 5 parts of polyol ester, four hexyl diphenylamines 0.05 of antioxidant
Part, 0.05 part of metal system sulfonate antirust agent, 0.05 part of phosphite ester compound extreme pressure anti-wear additives and succinic acid esters are ashless
It is 0.05 part of detergent dispersant to be uniformly mixed, be heated to 70 DEG C, cooling obtains lubricant oil composite.
Embodiment 2
Step 1, the preparation of modified vegetable oil: by weight, taking 120 parts of soybean oil, adds acid cation exchange
3 parts of resin, be warming up to 60 DEG C, be slowly added dropwise 10 parts of hydrogen peroxide, 6 parts of formic acid reacted, the reaction time be after being added dropwise again
It carries out 3 hours, after reaction, is washed, separate water layer, the modified soybean oil on upper layer carries out water with 60 DEG C of hot distilled water
It washes, discards water phase, then neutralized with alkali, then be washed to pH neutrality with distilled water and be modified after vacuum distillation removes moisture
Vegetable oil；
Step 2, by weight, by 40 parts of pentaerythrite, 30 parts of ethanedioic acid, 30 parts of oleanonic acid, 5 parts of catalyst,
120 parts of organic solvent are uniformly mixed, and then heat up, are reacted, the reaction time is 4 hours, 90 DEG C of reaction temperature, is steamed organic
Solvent obtains polyol ester；
Step 3, by weight, by 80 parts of modified vegetable oil, 10 parts of polyol ester, 1 part of four hexyl diphenylamines of antioxidant,
1 part of metal system sulfonate antirust agent, 1 part of phosphite ester compound extreme pressure anti-wear additives and the ashless system's cleaning dispersion of succinic acid esters
1 part of agent is uniformly mixed, and is heated to 120 DEG C, and cooling obtains lubricant oil composite.
Embodiment 3
Step 1, the preparation of modified vegetable oil: by weight, taking 110 parts of soybean oil, adds acid cation exchange
2 parts of resin, be warming up to 55 DEG C, be slowly added dropwise 8 parts of hydrogen peroxide, 5 parts of formic acid reacted, the reaction time be after being added dropwise again into
It row 2 hours, after reaction, is washed, separates water layer, the modified soybean oil on upper layer carries out water with 55 DEG C of hot distilled water
It washes, discards water phase, then neutralized with alkali, then be washed to pH neutrality with distilled water and be modified after vacuum distillation removes moisture
Vegetable oil；
Step 2, by weight, by 35 parts of pentaerythrite, 25 parts of ethanedioic acid, 25 parts of oleanonic acid, 4 parts of catalyst,
110 parts of organic solvent are uniformly mixed, and then heat up, are reacted, the reaction time is 3 hours, 80 DEG C of reaction temperature, is steamed organic
Solvent obtains polyol ester；
Step 3, by weight, by 72 parts of modified vegetable oil, 8 parts of polyol ester, four hexyl diphenylamines 0.06 of antioxidant
Part, 0.07 part of metal system sulfonate antirust agent, 0.08 part of phosphite ester compound extreme pressure anti-wear additives and succinic acid esters are ashless
It is 0.08 part of detergent dispersant to be uniformly mixed, be heated to 100 DEG C, cooling obtains lubricant oil composite.
Reference examples 1
Difference with embodiment 3 is: not being modified to soybean oil.
Step 1, by weight, by 35 parts of pentaerythrite, 25 parts of ethanedioic acid, 25 parts of oleanonic acid, 4 parts of catalyst,
110 parts of organic solvent are uniformly mixed, and then heat up, are reacted, the reaction time is 3 hours, 80 DEG C of reaction temperature, is steamed organic
Solvent obtains polyol ester；
Step 2 will pass through 72 parts of pretreated vegetable oil, 8 parts of polyol ester, four hexyl two of antioxidant by weight
0.06 part of aniline, 0.07 part of metal system sulfonate antirust agent, 0.08 part of phosphite ester compound extreme pressure anti-wear additives and succinic acid
Esters are ashless 0.08 part of system's detergent dispersant be uniformly mixed, be heated to 100 DEG C, it is cooling, obtain lubricant oil composite.
Reference examples 2
Difference with embodiment 3 is: soybean oil is without pretreatment.
The preparation of modified vegetable oil: step 1 by weight, takes without the pretreated soybean oil 110 of the above method
Part, add 2 parts of acid cation exchange resin, be warming up to 55 DEG C, be slowly added dropwise 8 parts of hydrogen peroxide, 5 parts of formic acid reacted,
Reaction time is to carry out again after being added dropwise 2 hours, after reaction, is washed, and water layer, the modified soybean oil on upper layer are separated
It is washed with 55 DEG C of hot distilled water, discards water phase, then neutralized with alkali, then be washed to pH neutrality, decompression with distilled water
After moisture is distilled off, modified vegetable oil is obtained；
Step 2, by weight, by 35 parts of pentaerythrite, 25 parts of ethanedioic acid, 25 parts of oleanonic acid, 4 parts of catalyst,
110 parts of organic solvent are uniformly mixed, and then heat up, are reacted, the reaction time is 3 hours, 80 DEG C of reaction temperature, is steamed organic
Solvent obtains polyol ester；
Step 3, by weight, by 72 parts of modified vegetable oil, 8 parts of polyol ester, four hexyl diphenylamines 0.06 of antioxidant
Part, 0.07 part of metal system sulfonate antirust agent, 0.08 part of phosphite ester compound extreme pressure anti-wear additives and succinic acid esters are ashless
It is 0.08 part of detergent dispersant to be uniformly mixed, be heated to 100 DEG C, cooling obtains lubricant oil composite.
Reference examples 3
Difference with embodiment 3 is: oleanonic acid is not added in step 2, but is all replaced with ethanedioic acid.
Step 1, the preparation of modified vegetable oil: by weight, taking 110 parts of soybean oil, adds acid cation exchange
2 parts of resin, be warming up to 55 DEG C, be slowly added dropwise 8 parts of hydrogen peroxide, 5 parts of formic acid reacted, the reaction time be after being added dropwise again into
It row 2 hours, after reaction, is washed, separates water layer, the modified soybean oil on upper layer carries out water with 55 DEG C of hot distilled water
It washes, discards water phase, then neutralized with alkali, then be washed to pH neutrality with distilled water and be modified after vacuum distillation removes moisture
Vegetable oil；
Step 2 by weight mixes 35 parts of pentaerythrite, 50 parts of ethanedioic acid, 4 parts of catalyst, 110 parts of organic solvent
It closes uniformly, then heats up, reacted, the reaction time is 3 hours, 80 DEG C of reaction temperature, steams organic solvent, obtains polyalcohol
Ester；
Step 3, by weight, by 72 parts of modified vegetable oil, 8 parts of polyol ester, four hexyl diphenylamines 0.06 of antioxidant
Part, 0.07 part of metal system sulfonate antirust agent, 0.08 part of phosphite ester compound extreme pressure anti-wear additives and succinic acid esters are ashless
It is 0.08 part of detergent dispersant to be uniformly mixed, be heated to 100 DEG C, cooling obtains lubricant oil composite.
Performance test
1, the wear-resistant test of high temperature
The wear-resistant test of high temperature of oil product is carried out using SRV frictional testing machine, experimental condition is load 300N, frequency
50Hz, stroke 1mm, 120 DEG C of temperature.
2, spot distributed test
Spot distributed test method is 1g program VG engine sludge to be added in 2g test oil, after ultrasonic disperse 6min,
Heat 2h in 200 DEG C of baking ovens, then by oil droplet on filter paper, after 24 hours measure oil mark dispersion loop diameter and greasy filth diameter it
Than as dispersion index.Dispersion index is higher, and the dispersibility for illustrating oil product is better.
3, QZX experiment
The equipment of use is the 25B-19 type coking plate instrument of Japanese Meitech company production, and the test simulation engine is bent
The operating condition of axle box and cylinder liner piston ring lubrication oil circulation makes the process for testing the constantly heated oxidation coking of oil product.When test
Between be 6h, oil temperature be 150 DEG C, plate temperature be 320 DEG C.
4, BRT ball rust test
BRT ball rust test is to replace program II D engine rig test, is mainly used to the anti-corruption of engine evaluated oil
Erosion and corrosion ability.During entire bench test in 18 hours, test oil guard metal ball continuous contact acidic liquid and
Air.Gray scale test is carried out by metal spherical reflector intensity after the end of the test, for determining corroded area, to evaluate examination
Test the resistant to rust ability of oil.Acetic acid/hydrobromic acid/hydrochloric acid/deionized water injection rate is 0.19 ml/hour, and air draught is
40 ml/mins, oil temperature are 48 DEG C.
5, biological degradability is the experiment side according to the CEC L-33-A-93(predecessor of the European Community for CEC L-33-T-82)
Method.
The result tested above is as shown in the table:
As can be seen from the table, methanol engine lubricating oil provided by the invention has good wear resistance；Especially
It is embodiment 3 for reference examples 1, having carried out epoxy-modified improve later to soybean oil can be improved its biodegrade
Speed, while can also improve greasy property.Embodiment 3 is for reference examples 2, after being pre-processed to soybean oil, energy
Enough improve wear-resisting property.Embodiment 3 joined oleanonic acid in the esterification reaction, be prepared for reference examples 3
Synthetic ester the greasy property of lubricating oil can be made to improve.
Claims (6)
1. a kind of preparation method of the degradable methanol engine lubricating oil of improved plant oil base, which is characterized in that including just like
Lower step:
Step 1, the preparation of modified vegetable oil: by weight, taking 100~120 parts of soybean oil, adds acid cation exchange
1~3 part of resin, heating, be slowly added dropwise 5~10 parts of hydrogen peroxide, 3~6 parts of formic acid reacted, after reaction, washed,
Separate water layer, the distilled water of the modified soybean oil heat on upper layer is washed, discard water phase, then neutralized with alkali, then with steam
Distilled water is washed to pH neutrality and obtains modified vegetable oil after vacuum distillation removes moisture；
Step 2, by weight, by 30~40 parts of polyalcohol, 20~30 parts of ethanedioic acid, 20~30 parts of oleanonic acid, catalysis
3~5 parts of agent, 80~120 parts of organic solvent be uniformly mixed, then heat up, reacted, steam organic solvent, obtain polyalcohol
Ester；
Step 3 by 70~80 parts of modified vegetable oil, 5~10 parts of polyol ester, 0.05~1 part of antioxidant, is prevented by weight
0.05~1 part of agent of rust, 0.05~1 part of extreme pressure anti-wear additives and 0.05~1 part of ashless system's detergent dispersant are uniformly mixed, and are heated to 70
It is~120 DEG C, cooling, obtain lubricant oil composite；
In the step 1, soybean oil is needed by pretreatment, and the preprocess method is as follows: taking 200mL soybean oil, adds
The ammonium hydroxide of the about 4wt% of oil volume a quarter is added in 20min, continues after adding when temperature rises to 35 DEG C for heat
15min is stirred, stirring is then stopped, being warming up to 95 DEG C, keeps 1h；Reaction mixture is poured into separatory funnel, stratification,
It separates and rinses oil reservoir with boiling water after soap stock water；The oil reservoir separated is warming up to 93~97 DEG C again, is added thereto in 10 minutes
The H of the 30wt% of oil volume 5%2O2, stop stirring, keep the temperature 1h at 120 DEG C；Stratification separates soap stock water with separatory funnel；
Oil reservoir, then stratification are rinsed with boiling water, water layer is removed, obtains pretreated soybean oil.
2. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, special
Sign is: in the step 1, heating is to make temperature to 50~60 DEG C, and the reaction time is that carry out 1~3 after being added dropwise again small
When.
3. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, special
Sign is: in the step 1,50~60 DEG C of temperature of the distilled water of the heat.
4. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, special
Sign is: in the step 2, the polyalcohol in hydroxymethyl-propane, glycerine, pentaerythrite, mannitol one
Kind or several mixing.
5. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, special
Sign is: the reaction time in the step 2 is 2~4 hours, 70~90 DEG C of reaction temperature.
6. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, special
Sign is: the extreme pressure anti-wear additives are phosphate compounds, phosphite ester compound, sulphur phosphorus complexing agent or sulfur-bearing extreme pressure
Agent.
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| CN107151577A (en) * | 2017-05-02 | 2017-09-12 | 长乐净能新材料科技有限公司 | A kind of preparation method of the vegetable oil based lubricating oil containing nano modified material |
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| US8357643B2 (en) * | 2004-08-10 | 2013-01-22 | Battelle Memorial Institute | Lubricants derived from plant and animal oils and fats |
| CN104450104A (en) * | 2014-12-27 | 2015-03-25 | 李康 | Method of preparing biodegradable lubricating oil |
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| US8357643B2 (en) * | 2004-08-10 | 2013-01-22 | Battelle Memorial Institute | Lubricants derived from plant and animal oils and fats |
| CN104450104A (en) * | 2014-12-27 | 2015-03-25 | 李康 | Method of preparing biodegradable lubricating oil |
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