CN105802697A - Method for preparing modified plant-oil-based degradable methanol engine lubricating oil - Google Patents
Method for preparing modified plant-oil-based degradable methanol engine lubricating oil Download PDFInfo
- Publication number
- CN105802697A CN105802697A CN201610176094.7A CN201610176094A CN105802697A CN 105802697 A CN105802697 A CN 105802697A CN 201610176094 A CN201610176094 A CN 201610176094A CN 105802697 A CN105802697 A CN 105802697A
- Authority
- CN
- China
- Prior art keywords
- oil
- parts
- lubricating oil
- preparation
- methanol engine
- 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.)
- Granted
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 28
- 239000010773 plant oil Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- -1 polyol ester Chemical class 0.000 claims abstract description 43
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 30
- 239000003549 soybean oil Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012153 distilled water Substances 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 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 claims abstract description 8
- 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
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 8
- 235000019253 formic acid Nutrition 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 43
- 235000019198 oils Nutrition 0.000 claims description 43
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 23
- 239000008158 vegetable oil Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 21
- 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
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- 239000003599 detergent Substances 0.000 claims description 12
- 239000013556 antirust agent Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 11
- 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
- 239000007866 anti-wear additive Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000002131 composite material Substances 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
- 238000001816 cooling Methods 0.000 claims description 9
- 238000013517 stratification Methods 0.000 claims description 9
- 229940059574 pentaerithrityl Drugs 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 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
- 239000005069 Extreme pressure additive Substances 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
- 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
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000013530 defoamer Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 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 7
- 150000003900 succinic acid esters Chemical class 0.000 description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 5
- 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 4
- 229920001577 copolymer Polymers 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 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
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002118 epoxides Chemical class 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
- 150000004867 thiadiazoles Chemical class 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 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
- 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
- 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
- 239000012964 benzotriazole Substances 0.000 description 2
- 150000003939 benzylamines Chemical class 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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000126 substance 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- DWLMIYNUGWGKQW-UHFFFAOYSA-N C(CCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCC)CCCC)CCCC Chemical class C(CCC)C=1C(=C(C(=C(C=1)NC1=CC=CC=C1)CCCC)CCCC)CCCC DWLMIYNUGWGKQW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 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
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 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 1
- 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
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GMEFLMYTWJUZQZ-UHFFFAOYSA-N n-benzyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC=CC=1CN(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1 GMEFLMYTWJUZQZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 150000005002 naphthylamines Chemical class 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012797 qualification Methods 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
- 239000001384 succinic acid Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/04—Fatty oil fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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Abstract
The invention relates to a method for preparing modified plant-oil-based degradable methanol engine lubricating oil and belongs to the technical field of lubricating oil.The method includes the steps that soybean oil is taken, acidic cation exchange resin is added, temperature is increased, hydrogen peroxide and formic acid are added dropwise for reaction, washing is conducted after reaction ends, a water layer is separated out, modified soybean oil on the upper layer is washed with hot distilled water, a water phase is discarded, neutralization is conducted with alkali, washing is conducted with distilled water till pH is neutral, and modified plant oil is obtained after water is removed through reduced pressure distillation; the modified plant oil, polyol ester, an antioxidant, an anti-rusting agent, anti-wear reagent at extreme pressure and an ashless cleaning dispersing agent are evenly mixed, heated and cooled, and a lubricating oil composition is obtained.The lubricating oil prepared through the method is suitable for a methanol engine, good in lubricating performance and biodegradable.
Description
Technical field
The preparation method that the present invention relates to the degradable methanol engine lubricating oil of a kind of improved plant oil base, belongs to technical field of lubricating oil.
Background technology
In automobilism the consumption costs of engine motor oil and little but it but affect the dynamic property of automobile, economy the more important thing is that it has influence on the functional reliability of electromotor and service life therefore according to the performance of electromotor, structure and correctly select machine oil particularly significant in conjunction with use condition.The effect of engine lubrication mainly includes: 1, lubrication: can make to stick to friction surface cambium layer oil film between machine oil engaging friction parts make two rubbing surfaces be not directly contacted with the fluid friction becoming between liquid oil layer by intermetallic dry friction as far as possible if can not get the profit essence that the parts that proper lubrication runs up will occur heat produced by metal and intermetallic dry friction friction that the metal molten of rubbing surface can be made within very short time to make parts stuck and good during electromotor work；2, cooling effect: during electromotor work, maximum combustion temperature is likely to up to 2400 DEG C, even if in the mean temperature of idling speed lower combustion chamber also more than 1000 DEG C, the part contacted with high-temperature fuel gas be subject to heat intensive now must carry out treating but otherwise electromotor to be stranded temperature too high and burn out；3, rust inhibition: parts generation corrosiveness machine oil can be adsorbed on metal surface and prevent sour gas and water to corrosion of metal by the sour gas cognition produced when the water of electromotor air when working or depositing and burning.
Along with industrialized continuous progress, the demand of the energy is increased day by day, energy problem has become the big factors of restriction economic development, therefore, the research of the substitute fuel of petroleum replacing and use, obtaining fast development, at present, technically the substitute fuel of comparatively molding has: methanol, ethanol are the substitute fuel of gasoline；(such as: China's most area promotes 10% ethanol petrol) dimethyl ether, monoesters are the alternative fuel of diesel oil；As can be seen here, alcohol ethers fuel as an alternative has become as main flow, alcohol ethers fuel as an alternative, although serving certain effect to alleviating energy scarcity, but its some technical problem in popularization should cause enough attention.Especially alcohol ether class A fuel A in use engine lubricating oil is formed in the decomposition of important additives ZDDP (zinc dialkyl dithiophosphate), have a strong impact on the antioxygenic property of former engine lubricating oil, its oil draining period is made to be greatly shortened, engine intake valve carbon distribution generates tendency and is greatly increased, and long-term accumulated can have a strong impact on the serviceability of electromotor.
CN103897775A discloses a kind of different proportion alcohol engine oil ageing inhibitor and preparation method thereof.The present invention is dredged one group of compound additive of base thiadiazoles 3～35%, amido borate 10～60%, modified low alkali value calcium mahogany sulfonate 15～40%, flux oil 5～10% composition by N-phenyl-α naphthylamine 5～45%, 2,5-.The preparation method is that: by flux oil heating 55～65 DEG C so far, be then separately added into N-phenyl-α naphthylamine, 2,5-thin base thiadiazoles, amido borate, modified low alkali value calcium mahogany sulfonate constant temperature 45～50 DEG C stirring successively no less than 45min.CN105176637A discloses a kind of bio-based methanol gasoline engine specific complex lubricating oil and preparation method thereof.Base oil is squeezed in the reactor device of heated and stirred, to heat to 75 DEG C by the present invention, and constant temperature stirs 1 hour；Being subsequently adding viscosity modified component, heat to 80 DEG C, constant temperature stirs 30 minutes；By the mixture temperature drop that obtains to 75 DEG C, add the antirust component of antioxygen, antioxygen anti-glue component, auxiliary antioxygen component, metal detergent component, ashless dispersants component, extreme-pressure anti-wear component, metal anti-attrition component, anti-breast breakdown of emulsion component, pour point depression component and oily components and stir 20 minutes at 75 DEG C；It is subsequently adding anti-bubble component to stir 30 minutes；Filter after finally the mixture cutter obtained is done pre-shearing 1 hour, detect, settle 24 hours in settling tank, to obtain final product.
But the cost of material of above-mentioned lubricating oil is high, and yet suffer from, when using in Alcohol engines, the problem that abrasion resistance is bad；And above-mentioned engine lubricating oil can not biodegradation preferably, environment can be affected.
Summary of the invention
It is an object of the invention to: provide a kind of lubricating oil being applied to methanol engine, this lubricating oil needs have good biodegradable, and this lubricating oil is that oil prepares based on epoxide modified vegetable oil.
Technical scheme is as follows:
The preparation method of the degradable methanol engine lubricating oil of a kind of improved plant oil base, comprises the following steps that
1st step, the preparation of modified vegetable oil: by weight, take soybean oil 100～120 parts, add acid cation exchange resin 1～3 part, heat up, be slowly added dropwise hydrogen peroxide 5～10 parts, 3～6 parts of formic acid reacts, reaction is washed, is separated water layer after terminating, the distilled water of the modified soybean oil heat on upper strata is washed, aqueous phase discarded, then be neutralized with alkali, then it is washed to pH neutrality with distilled water, decompression obtains modified vegetable oil after moisture is distilled off；
2nd step, by weight, by polyhydric alcohol 30～40 parts, ethanedioic acid 20～30 parts, oleanonic acid 20～30 parts, catalyst 3～5 parts, 80～120 parts of mix homogeneously of organic solvent, then heats up, reacts, steam organic solvent, obtain polyol ester；
3rd step, by weight, by modified vegetable oil 70～80 parts, polyol ester 5～10 parts, 0.05～1 part of antioxidant, antirust agent 0.05～1 part, extreme pressure anti-wear additives 0.05～1 part and 0.05～1 part of mix homogeneously of ashless system detergent dispersant, heating is to 70～120 DEG C, cooling, obtains lubricant oil composite.
In the 1st described step, intensification is to make temperature to 50～60 DEG C, and the response time is to carry out 1～3 hour after dropwising again.In the 1st described step, the temperature 50～60 DEG C of the distilled water of described heat.
In the 2nd described step, the mixing of one or more in hydroxymethyl-propane, glycerol, tetramethylolmethane, mannitol of the described polyhydric alcohol.
The described response time in the 2nd step is 2～4 hours, reaction temperature 70～90 DEG C.
Described extreme pressure anti-wear additives is phosphate compounds, phosphite ester compound, sulfur phosphorus complexing agent or sulfur-containing extreme-pressure additive.
In the 1st described step, soybean oil needs through pretreatment, described preprocess method is as follows: take 200mL soybean oil, heating, when temperature rises to 35 DEG C, adds the ammonia of the 4wt% being about oil volume 1/4th in 20min, stirring 15min is continued after adding, then turn off stirring, be warming up to 95 DEG C, keep 1h；Reaction mixture is poured in separatory funnel, stratification, after separating soap stock water, rinse oil reservoir with boiling water；The oil reservoir separated is warming up to 93～97 DEG C again, in 10 minutes, is added thereto to the H of the 30wt% of oil volume 5%2O2, stop stirring, at 120 DEG C, be incubated 1h；Stratification, separates soap stock water with separatory funnel；Rinse oil reservoir then stratification with boiling water, remove water layer, obtain pretreated soybean oil.
Beneficial effect
The lubricating oil that the present invention prepares is suitable for methanol engine, and greasy property is good, biodegradable.
Detailed description of the invention
In the lubricant oil composite that the present invention adopts, by soybean oil being carried out epoxide modified its biodegradation rate that can improve, also can improve greasy property simultaneously.Polyol ester is basic components, adds oleanonic acid and can improve biological degradability in its preparation process.
It addition, organic solvent is not particularly limited in ester fat course of reaction, it is possible to enumerate the alcohols such as the arene compounds such as the alkanes such as hexane, hexamethylene, heptane, toluene, dimethylbenzene, methanol, ethanol, isopropanol, butanol, hexanol, Hexalin.It addition, the nitrile compounds such as ester compounds, acetonitrile etc. such as the ethers such as the ketones such as butanone, methyl iso-butyl ketone (MIBK), cycloheptanone, Ketohexamethylene, ether, oxolane, dioxane, ethyl acetate, butyl acetate, methyl formate according to circumstances can also be used.
In the lubricant oil composite prepared, do not damaging within the scope of the object of the invention, various additive can be added as required, for instance: at least one selected in ashless system detergent dispersant, antioxidant, antirust agent, metal deactivator, viscosity index improver, flow point depressant and defoamer etc..
Herein, ashless system detergent dispersant can be enumerated, for instance: the unitary or dicarboxylic acids amide-type etc. representated by butanimide class, boracic butanimide class, benzylamine class, boracic benzylamine class, succinic acid esters, fatty acid or succinic acid.The combined amount of ashless system detergent dispersant, considers from the balance of effect and economy, with the total amount of compositions for benchmark, in more than 0.01wt%, below 5wt% left and right.
As antioxidant, it is possible to use amine system antioxidant, phenol system antioxidant and the sulfur system antioxidant used in existing lubricating oil.These antioxidants can be used alone a kind or combine two or more use.Enumerate as amine system antioxidant, for instance: the monoalkyl diphenylamines based compounds 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 diphenylamine, 4, the dialkyl diphenylamine based compound such as 4 '-dinonyldiphenylamine；The poly-alkyl diphenyl amine compounds such as tetrabutyl diphenylamines, four hexyl diphenylamines, four octyl diphenylamines, four nonyl diphenylamine；The naphthylamines based compounds such as alpha-naphthylamine, phenyl-a-naphthylamine, butyl phenyl-alpha-naphthylamine, benzyl phenyl-alpha-naphthylamine, hexyl phenyl-a-naphthylamine, heptyl phenyl-a-naphthylamine, octyl phenyl-alpha-naphthylamine, nonyl phenyl-a-naphthylamine.Phenol system antioxidant can be enumerated, such as: 2,6-di-t-butyl-4-aminomethyl phenyl, 2,6-di-t-butyl-4-ethylphenyl, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) the monophenol based compound such as propionic ester, 4,4 '-di-2-ethylhexylphosphine oxide-(2,6-DI-tert-butylphenol compounds), 2, the biphenol based compound such as 2 '-di-2-ethylhexylphosphine oxide-(4-ethyl-6-tert-butyl phenol).
Sulfur system antioxidant can be enumerated, such as 2,6-di-t-butyl-4-(4, double; two (octylsulfo)-1 of 6-, 3,5-triazine-2-base amino) phenol, Phosphoric sulfide and pinene the dialkyl dipropionates etc. such as sulfo-terpene hydrocarbon-based compound, two lauryl alcohol thiodipropionates, distearyl alcohol thiodipropionate such as reactant.
Antirust agent can enumerate metal system sulfonate, alkenyl succinic acid ester etc..The combined amount of these antirust agent, from the viewpoint of mixed effect, with total composition for benchmark, is approximately in more than 0.01wt%, below 0.5wt%.
As metal deactivator (copper anticorrosive), it is possible to enumerate, for instance: benzotriazole system, tolyl-triazole system, thiadiazoles system, imidazoles system and pyrimidine compound etc..Wherein, it is preferable that benzotriazole based compound.The combined amount of these metal deactivators, from the viewpoint of mixed effect, with total composition for benchmark, is approximately in more than 0.01wt%, below 0.1wt%.
As viscosity index improver, can enumerate, such as: polymethacrylates, decentralized polymethacrylates, olefin copolymer (e.g., ethylene-propylene copolymer etc.), decentralized olefin copolymer, styrene based copolymer (such as styrenic-diene copolymer, styrene-isoprene copolymer etc.) etc..The combined amount of these viscosity index improvers, from the viewpoint of mixed effect, with total composition for benchmark, is approximately in more than 0.5wt%, below 15wt%.
Flow point depressant can be enumerated: the condensation substance of the condensation substance of ethylene-vinyl acetate copolymer, chlorinated paraffin and naphthalene, chlorinated paraffin and phenol, polymethacrylates, alkyl styrenes etc., for instance, it may be preferable to use matter average molecular weight more than 50,000, the polymethacrylates of about less than 150,000.The combined amount of flow point depressant, with total composition for benchmark, is approximately in more than 0.1wt%, below 5wt%.
Defoamer preferred polymeric silicone system defoamer, polyacrylate system defoamer, can play defoaming effectively by mixing this polymeric silicone system defoamer etc..Such polymeric silicone system defoamer can enumerate such as organopolysiloxane, is especially suitable for the fluorine-containing organopolysiloxanes such as three fluoro hydroxypropyl methyl silicone oil.The combined amount of defoamer, considers from the balance of defoaming effect and economy, with the total amount of compositions for benchmark, is approximately in more than 0.005wt%, below 0.1wt%.
The Biodegradable lubricant composition of the present invention, because lubricity, oxidation stability and biological degradability are excellent, so the use can being applied to aptly in such as methanol engine.
The soybean oil adopted in following example is through pretreatment, described preprocess method is as follows: take 200mL soybean oil, heating, when temperature rises to 35 DEG C, in 20min, add the ammonia of the 4wt% being about oil volume 1/4th, continue stirring 15min after adding, then turn off stirring, it is warming up to 95 DEG C, keeps 1h；Reaction mixture is poured in separatory funnel, stratification, after separating soap stock water, rinse oil reservoir with boiling water；The oil reservoir separated is warming up to 93～97 DEG C again, in 10 minutes, is added thereto to the H of the 30wt% of oil volume 5%2O2, stop stirring, at 120 DEG C, be incubated 1h；Stratification, separates soap stock water with separatory funnel；Rinse oil reservoir then stratification with boiling water, remove water layer, obtain pretreated soybean oil.
In following example, the catalyst used by the 2nd step esterification is solid super acid catalyst SO4 2-/ZrO2。
Embodiment 1
1st step, the preparation of modified vegetable oil: by weight, take soybean oil 100 parts, add acid cation exchange resin 1 part, it is warming up to 50 DEG C, be slowly added dropwise hydrogen peroxide 5 parts, 3 parts of formic acid reacts, and the response time is to carry out 1 hour after dropwising again, after reaction terminates, wash, separating water layer, the modified soybean oil on upper strata is washed with distilled water 50 DEG C hot, aqueous phase discarded, it is neutralized with alkali again, being washed to pH neutrality with distilled water again, decompression obtains modified vegetable oil after moisture is distilled off；
2nd step, by weight, by tetramethylolmethane 30 parts, ethanedioic acid 20 parts, oleanonic acid 20 parts, catalyst 3～5 parts, 80 parts of mix homogeneously of organic solvent, then heating up, react, the response time is 2 hours, reaction temperature 70 DEG C, steams organic solvent, obtains polyol ester；
3rd step, by weight, by modified vegetable oil 70 parts, polyol ester 5 parts, antioxidant four hexyl diphenylamines 0.05 part, metal system sulfonate antirust agent 0.05 part, phosphite ester compound extreme pressure anti-wear additives 0.05 part and succinic acid esters ashless system 0.05 part of mix homogeneously of detergent dispersant, heating is to 70 DEG C, cooling, obtains lubricant oil composite.
Embodiment 2
1st step, the preparation of modified vegetable oil: by weight, take soybean oil 120 parts, add acid cation exchange resin 3 parts, it is warming up to 60 DEG C, be slowly added dropwise hydrogen peroxide 10 parts, 6 parts of formic acid reacts, and the response time is to carry out 3 hours after dropwising again, after reaction terminates, wash, separating water layer, the modified soybean oil on upper strata is washed with distilled water 60 DEG C hot, aqueous phase discarded, it is neutralized with alkali again, being washed to pH neutrality with distilled water again, decompression obtains modified vegetable oil after moisture is distilled off；
2nd step, by weight, by tetramethylolmethane 40 parts, ethanedioic acid 30 parts, oleanonic acid 30 parts, catalyst 5 parts, 120 parts of mix homogeneously of organic solvent, then heating up, react, the response time is 4 hours, reaction temperature 90 DEG C, steams organic solvent, obtains polyol ester；
3rd step, by weight, by modified vegetable oil 80 parts, polyol ester 10 parts, antioxidant four hexyl diphenylamines 1 part, metal system sulfonate antirust agent 1 part, phosphite ester compound extreme pressure anti-wear additives 1 part and succinic acid esters ashless system 1 part of mix homogeneously of detergent dispersant, heating is to 120 DEG C, cooling, obtains lubricant oil composite.
Embodiment 3
1st step, the preparation of modified vegetable oil: by weight, take soybean oil 110 parts, add acid cation exchange resin 2 parts, it is warming up to 55 DEG C, be slowly added dropwise hydrogen peroxide 8 parts, 5 parts of formic acid reacts, and the response time is to carry out 2 hours after dropwising again, after reaction terminates, wash, separating water layer, the modified soybean oil on upper strata is washed with distilled water 55 DEG C hot, aqueous phase discarded, it is neutralized with alkali again, being washed to pH neutrality with distilled water again, decompression obtains modified vegetable oil after moisture is distilled off；
2nd step, by weight, by tetramethylolmethane 35 parts, ethanedioic acid 25 parts, oleanonic acid 25 parts, catalyst 4 parts, 110 parts of mix homogeneously of organic solvent, then heating up, react, the response time is 3 hours, reaction temperature 80 DEG C, steams organic solvent, obtains polyol ester；
3rd step, by weight, by modified vegetable oil 72 parts, polyol ester 8 parts, antioxidant four hexyl diphenylamines 0.06 part, metal system sulfonate antirust agent 0.07 part, phosphite ester compound extreme pressure anti-wear additives 0.08 part and succinic acid esters ashless system 0.08 part of mix homogeneously of detergent dispersant, heating is to 100 DEG C, cooling, obtains lubricant oil composite.
Reference examples 1
It is distinctive in that with embodiment 3: soybean oil is not modified.
1st step, by weight, by tetramethylolmethane 35 parts, ethanedioic acid 25 parts, oleanonic acid 25 parts, catalyst 4 parts, 110 parts of mix homogeneously of organic solvent, then heating up, react, the response time is 3 hours, reaction temperature 80 DEG C, steams organic solvent, obtains polyol ester；
2nd step, by weight, by through the vegetable oil 72 parts of pretreatment, polyol ester 8 parts, antioxidant four hexyl diphenylamines 0.06 part, metal system sulfonate antirust agent 0.07 part, phosphite ester compound extreme pressure anti-wear additives 0.08 part and succinic acid esters ashless system 0.08 part of mix homogeneously of detergent dispersant, heating is to 100 DEG C, cooling, obtains lubricant oil composite.
Reference examples 2
It is distinctive in that with embodiment 3: soybean oil is without pretreatment.
1st step, the preparation of modified vegetable oil: by weight, take the soybean oil 110 parts without said method pretreatment, add acid cation exchange resin 2 parts, it is warming up to 55 DEG C, be slowly added dropwise hydrogen peroxide 8 parts, 5 parts of formic acid reacts, and the response time is to carry out 2 hours after dropwising again, after reaction terminates, wash, separating water layer, the modified soybean oil on upper strata is washed with distilled water 55 DEG C hot, aqueous phase discarded, it is neutralized with alkali again, being washed to pH neutrality with distilled water again, decompression obtains modified vegetable oil after moisture is distilled off；
2nd step, by weight, by tetramethylolmethane 35 parts, ethanedioic acid 25 parts, oleanonic acid 25 parts, catalyst 4 parts, 110 parts of mix homogeneously of organic solvent, then heating up, react, the response time is 3 hours, reaction temperature 80 DEG C, steams organic solvent, obtains polyol ester；
3rd step, by weight, by modified vegetable oil 72 parts, polyol ester 8 parts, antioxidant four hexyl diphenylamines 0.06 part, metal system sulfonate antirust agent 0.07 part, phosphite ester compound extreme pressure anti-wear additives 0.08 part and succinic acid esters ashless system 0.08 part of mix homogeneously of detergent dispersant, heating is to 100 DEG C, cooling, obtains lubricant oil composite.
Reference examples 3
It is distinctive in that with embodiment 3: the 2nd step does not add oleanonic acid, but all replaces with ethanedioic acid.
1st step, the preparation of modified vegetable oil: by weight, take soybean oil 110 parts, add acid cation exchange resin 2 parts, it is warming up to 55 DEG C, be slowly added dropwise hydrogen peroxide 8 parts, 5 parts of formic acid reacts, and the response time is to carry out 2 hours after dropwising again, after reaction terminates, wash, separating water layer, the modified soybean oil on upper strata is washed with distilled water 55 DEG C hot, aqueous phase discarded, it is neutralized with alkali again, being washed to pH neutrality with distilled water again, decompression obtains modified vegetable oil after moisture is distilled off；
2nd step, by weight, by tetramethylolmethane 35 parts, ethanedioic acid 50 parts, catalyst 4 parts, 110 parts of mix homogeneously of organic solvent, then heats up, reacts, and the response time is 3 hours, reaction temperature 80 DEG C, steams organic solvent, obtains polyol ester；
3rd step, by weight, by modified vegetable oil 72 parts, polyol ester 8 parts, antioxidant four hexyl diphenylamines 0.06 part, metal system sulfonate antirust agent 0.07 part, phosphite ester compound extreme pressure anti-wear additives 0.08 part and succinic acid esters ashless system 0.08 part of mix homogeneously of detergent dispersant, heating is to 100 DEG C, cooling, obtains lubricant oil composite.
Performance test
1, high temperature resistance to wears test
Adopting SRV frictional testing machine to carry out the high temperature of oil product to resistance to wear test, experimental condition is load 300N, frequency 50Hz, stroke 1mm, temperature 120 DEG C.
2, speckle distributed test
Speckle distributed test method is 1g program VG engine sludge to add 2g test in oil, after ultrasonic disperse 6min, heats 2h in 200 DEG C of baking ovens, then by oil droplet on filter paper, measures oil mark circle of dispersion diameter and greasy filth diameter ratio, be dispersion index after 24 hours.The dispersibility of the more high explanation oil product of dispersion index is more good.
3, QZX experiment
The equipment adopted is the 25B-19 type coking plate instrument that Meitech company of Japan produces, the working condition of this test simulation engine crankcase and cylinder liner piston ring lubrication oil circulation, makes test oil product constantly be heated and aoxidizes the process of coking.Test period is 6h, and oil temperature is 150 DEG C, and plate temperature is 320 DEG C.
4, BRT ball rust test
BRT ball rust test is that instead of program IID engine rig test, is mainly used to the anticorrosive and corrosion ability of engine evaluated oil.In the bench test process of whole 18 hours, test metal ball continuous contact acidic liquid and the air of oil guard.After off-test, carry out gray scale test by metal ball reflecting surface intensity, be used for determining corroded area, thus the resistant to rust ability of qualification test oil.Acetic acid/hydrobromic acid/hydrochloric acid/deionized water injection rate is 0.19 ml/hour, and air draught is 40 ml/min, and oil temperature is 48 DEG C.
5, biological degradability is the CECL-33-A-93(predecessor according to the European Community is CECL-33-T-82) experimental technique.
The result more than tested 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；Particularly embodiment 3 is relative to reference examples 1, soybean oil has carried out epoxide modified improve afterwards and can improve its biodegradation rate, also can improve greasy property simultaneously.Embodiment 3 is relative to reference examples 2, after soybean oil is carried out pretreatment, it is possible to increase anti-wear performance.Embodiment 3, relative to reference examples 3, adds oleanonic acid in the esterification reaction, and the synthetic ester prepared can make the greasy property of lubricating oil improve.
Claims (7)
1. the preparation method of the degradable methanol engine lubricating oil of an improved plant oil base, it is characterised in that comprise the following steps that
1st step, the preparation of modified vegetable oil: by weight, take soybean oil 100～120 parts, add acid cation exchange resin 1～3 part, heat up, be slowly added dropwise hydrogen peroxide 5～10 parts, 3～6 parts of formic acid reacts, reaction is washed, is separated water layer after terminating, the distilled water of the modified soybean oil heat on upper strata is washed, aqueous phase discarded, then be neutralized with alkali, then it is washed to pH neutrality with distilled water, decompression obtains modified vegetable oil after moisture is distilled off；
2nd step, by weight, by polyhydric alcohol 30～40 parts, ethanedioic acid 20～30 parts, oleanonic acid 20～30 parts, catalyst 3～5 parts, 80～120 parts of mix homogeneously of organic solvent, then heats up, reacts, steam organic solvent, obtain polyol ester；
3rd step, by weight, by modified vegetable oil 70～80 parts, polyol ester 5～10 parts, 0.05～1 part of antioxidant, antirust agent 0.05～1 part, extreme pressure anti-wear additives 0.05～1 part and 0.05～1 part of mix homogeneously of ashless system detergent dispersant, heating is to 70～120 DEG C, cooling, obtains lubricant oil composite.
2. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, it is characterised in that: in the 1st described step, intensification is to make temperature to 50～60 DEG C, and the response time is to carry out 1～3 hour after dropwising again.
3. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, it is characterised in that: in the 1st described step, the temperature 50～60 DEG C of the distilled water of described heat.
4. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, it is characterized in that: in the 2nd described step, the mixing of one or more in hydroxymethyl-propane, glycerol, tetramethylolmethane, mannitol of the described polyhydric alcohol.
5. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, it is characterised in that: the described response time in the 2nd step is 2～4 hours, reaction temperature 70～90 DEG C.
6. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, it is characterised in that: described extreme pressure anti-wear additives is phosphate compounds, phosphite ester compound, sulfur phosphorus complexing agent or sulfur-containing extreme-pressure additive.
7. the preparation method of the degradable methanol engine lubricating oil of improved plant oil base according to claim 1, it is characterized in that: in the 1st described step, soybean oil needs through pretreatment, and described preprocess method is as follows: take 200mL soybean oil, heating, when temperature rises to 35 DEG C, in 20min, add the ammonia of the 4wt% being about oil volume 1/4th, continue stirring 15min after adding, then turn off stirring, it is warming up to 95 DEG C, keeps 1h；Reaction mixture is poured in separatory funnel, stratification, after separating soap stock water, rinse oil reservoir with boiling water；The oil reservoir separated is warming up to 93～97 DEG C again, in 10 minutes, is added thereto to the H of the 30wt% of oil volume 5%2O2, stop stirring, at 120 DEG C, be incubated 1h；Stratification, separates soap stock water with separatory funnel；Rinse oil reservoir then stratification with boiling water, remove water layer, obtain pretreated soybean oil.
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| CN106753710A (en) * | 2016-11-30 | 2017-05-31 | 南京悠谷知识产权服务有限公司 | A kind of preparation method of the good lubricating oil used for natural gas engine of anti-nitrification property |
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| CN108914689A (en) * | 2017-10-11 | 2018-11-30 | 天津中天精科科技有限公司 | A kind of paper for daily use paper pulp release agent and its preparation process |
| CN109652173A (en) * | 2018-11-01 | 2019-04-19 | 苏州玖城润滑油有限公司 | The preparation method of PERFORMANCE OF MODIFIED VERMICULITE base grease |
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