CN116064188A - 润滑油组合物及其制备方法 - Google Patents
润滑油组合物及其制备方法 Download PDFInfo
- Publication number
- CN116064188A CN116064188A CN202111300046.1A CN202111300046A CN116064188A CN 116064188 A CN116064188 A CN 116064188A CN 202111300046 A CN202111300046 A CN 202111300046A CN 116064188 A CN116064188 A CN 116064188A
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- China
- Prior art keywords
- polyisobutene
- lubricating oil
- calcium
- oil composition
- detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title description 3
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 48
- 239000003599 detergent Substances 0.000 claims abstract description 37
- 239000002199 base oil Substances 0.000 claims abstract description 29
- 230000001050 lubricating effect Effects 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- -1 calcium sulfophosphonate Chemical compound 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 57
- 239000011575 calcium Substances 0.000 claims description 33
- 229910052791 calcium Inorganic materials 0.000 claims description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HGFSRWCYBXZETH-UHFFFAOYSA-L P([O-])([O-])=S.[Ca+2] Chemical compound P([O-])([O-])=S.[Ca+2] HGFSRWCYBXZETH-UHFFFAOYSA-L 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012990 dithiocarbamate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 claims description 2
- LJKQIQSBHFNMDV-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound C1=CC=CC2(O)C1S2 LJKQIQSBHFNMDV-UHFFFAOYSA-N 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims 1
- 229960001860 salicylate Drugs 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000010727 cylinder oil Substances 0.000 description 33
- 239000008186 active pharmaceutical agent Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000013022 formulation composition Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- ZNCAMSISVWKWHL-UHFFFAOYSA-L zinc;butoxy-butylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([O-])(=S)SCCCC.CCCCOP([O-])(=S)SCCCC ZNCAMSISVWKWHL-UHFFFAOYSA-L 0.000 description 2
- GBEDXBRGRSPHRI-UHFFFAOYSA-L zinc;octoxy-octylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCOP([O-])(=S)SCCCCCCCC.CCCCCCCCOP([O-])(=S)SCCCCCCCC GBEDXBRGRSPHRI-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- NRINZBKAERVHFW-UHFFFAOYSA-L zinc;dicarbamate Chemical compound [Zn+2].NC([O-])=O.NC([O-])=O NRINZBKAERVHFW-UHFFFAOYSA-L 0.000 description 1
- QUPAJUAGQJQKQE-UHFFFAOYSA-L zinc;n,n-dipropylcarbamodithioate Chemical compound [Zn+2].CCCN(C([S-])=S)CCC.CCCN(C([S-])=S)CCC QUPAJUAGQJQKQE-UHFFFAOYSA-L 0.000 description 1
- JAAZVYLRCFILFJ-UHFFFAOYSA-L zinc;oxido-phenoxy-phenylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].C=1C=CC=CC=1SP(=S)([O-])OC1=CC=CC=C1.C=1C=CC=CC=1SP(=S)([O-])OC1=CC=CC=C1 JAAZVYLRCFILFJ-UHFFFAOYSA-L 0.000 description 1
- LZVDFWITYZHIEU-UHFFFAOYSA-L zinc;oxido-propoxy-propylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCOP([O-])(=S)SCCC.CCCOP([O-])(=S)SCCC LZVDFWITYZHIEU-UHFFFAOYSA-L 0.000 description 1
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
-
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
本发明提出了一种润滑油组合物,包括复合清净剂、复合分散剂、二烷基二硫代磷酸锌和/或二烷基二硫代氨基甲酸锌、润滑基础油;其中所述复合清净剂为超高碱值清净剂和中低碱值清净剂的混合物,所述复合分散剂为聚异丁烯硫膦酸钙和聚异丁烯马来酸酐的混合物。本发明的润滑油组合物具有优异的高温清净性、氧化安定性、酸中和性、抗磨减摩性、储存稳定性,适用于船用柴油发动机的润滑,特别适用于二冲程低速十字头船用柴油机的润滑。
Description
技术领域
本发明涉及润滑油领域,特别涉及一种适用于船用柴油发动机的润滑油组合物及其制备方法。
背景技术
随着我国海洋运输业迅速发展,大型船舶船用油的需求量不断增加,油品质量不断提高,尤其是气缸油的要求越来越高。气缸油一般用于远洋大型货轮(VLCC)的二冲程的低速十字头发动机润滑,发动机功率大、工作温度高,需要燃烧重质、高硫(硫含量在2.5%~4%)燃料,燃烧时会产生大量的酸性物质,极易对气缸套、活塞环及活塞造成腐蚀磨损。因此船用气缸油要有足够的有效碱值中和燃烧中产生的酸性物质,要有足够的承载能力,需要最大限度地减少活塞环与缸套之间的摩擦磨损;要求气缸油有一定的扩散性,使气缸油能迅速地扩散到整个气缸表面,避免形成干摩擦;要求气缸油有良好的清净分散性能,从而可以有效地防止活塞环槽和进排气门积炭;要求气缸油具有好的储存稳定性,能长期储存而不变质,与其它品牌气缸油的混兑性能良好,不产生沉淀。
目前,气缸油的碱值一般为40~100mgKOH/g,其中40TBN、70TBN碱值的气缸油用量最大,配方一般以清净剂为主,其它添加剂为辅,其中高温清净性和抗磨性是两个重要指标。清净剂及基础油的性能直接关系到气缸油性能的好坏。清净剂的加入量也直接关系到配方的经济性,因此,采用性能更好的清净剂、基础油及降低使用配方剂量是近年来船用气缸油的研发热点。
CN 101570712《一种高碱值船用气缸润滑油》公开了一种基础油为中间基基础油、金属清净剂为环烷酸钙的40TBN船用高碱值船用气缸润滑油,按重量百分比,含有环烷酸钙0.2%~25%、硫化烷基酚钙0.2%~20%、丁二酰亚胺0.2%~20%、磷酸三甲酚脂或苯三唑脂肪胺盐0.05%~15%、氨基甲酸锌0.1%~18%、烷基萘0.1%~16%、二甲基硅0.0001%~0.1%、聚醚0.01%~5%和基础油,具有较好的扩散性、抗水性、抗腐蚀磨损性和清净性。
US 8980805公开了一种用于高低硫燃料的船用润滑剂,是一种40TBN船用气缸油,其中含有0.1%~2%的金属清净剂,在燃烧高硫燃料时具有较好的酸中和性。US 8334245《两冲程船用气缸油》公开了一种40TBN以上的船用气缸油,其中包括至少一种润滑油基础油,至少一种清净剂,对于高硫燃料燃烧时形成的硫酸具有较强的中和能力。
以上研究报道的气缸油在大部分场合能满足发动机的工作要求。但是,配方中使用的清净剂的加入量较大、配方成本较高。最近几年,随着超高碱值清净剂的开发,船用气缸油的配方进一步得到优化,其中采用碱值大于590mgKOH/g的超高碱值磺酸钙取代其它磺酸钙,在各项性能不变的前提下,配方的剂量显著降低,生产成本大大降低。但是在使用中发现,采用高碱值磺酸钙的气缸油的外观不好,尤其是超高碱值磺酸钙与二烷基二硫代磷酸锌、二烷基二硫代氨基甲酸锌共同存在时出现浑浊甚至沉淀现象。而不采用这两种添加剂复配,配方性能不好。因此,现有的配方技术需要改进。
另外,随着发动机功率的增加、油品换油周期的延长,要求原有油品的清净性、抗磨性、抗氧化性、分散性也要进一步提高,现有配方中的各项性能也需要进一步改进。
发明内容
为了克服现有技术中存在的缺陷,本发明提出了一种润滑油组合物及其制备方法。
本发明的润滑油组合物,包括复合清净剂、复合分散剂、二烷基二硫代磷酸锌和/或二烷基二硫代氨基甲酸锌、润滑基础油;其中所述复合清净剂为超高碱值清净剂和中低碱值清净剂的混合物,所述复合分散剂为聚异丁烯硫膦酸钙和聚异丁烯马来酸酐的混合物。
根据本发明,所述的超高碱值清净剂优选选自碱值大于590mgKOH/g的磺酸钙;所述的中低碱值清净剂优选选自碱值为20~150mgKOH/g的烷基苯磺酸钙、磺酸锂、烷基水杨酸钙和硫化烷基酚钙中的一种或多种。
根据本发明,在所述复合清净剂中,所述超高碱值清净剂与中低碱值清净剂的质量比优选为1:0.1~0.5。
根据本发明,所述聚异丁烯硫膦酸钙中聚异丁烯的数均分子量优选为300~10000,更优选400~5000,进一步优选500~3000。
根据本发明,所述聚异丁烯硫膦酸钙的优选制备方法包括:使聚异丁烯与P2S5反应生成聚异丁烯硫膦酸酐,然后与水反应生成聚异丁烯硫膦酸,再与氢氧化钙反应,收集产物。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,所述聚异丁烯的数均分子量优选为300~10000,更优选400~5000,进一步优选500~3000。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,聚异丁烯与P2S5反应的温度优选为150~250℃,反应时间优选为1~15h。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,所述聚异丁烯硫膦酸酐与水反应的温度优选为100~250℃(水以水蒸汽的形式存在),反应时间优选为1~20h。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,所述聚异丁烯硫膦酸与氢氧化钙反应的温度优选为50~200℃,反应时间优选为1~8h。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,所述聚异丁烯、P2S5、水、氢氧化钙之间的摩尔比优选为1~5:1~3:1~3:1~3。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,在所述聚异丁烯硫膦酸与氢氧化钙的反应中,任选加入稀释油,所述稀释油优选API I类油和/或API II类油,所述稀释油的加入量优选为所述聚异丁烯质量的50%~200%。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,在所述聚异丁烯硫膦酸与氢氧化钙的反应中,任选加入低分子醇促进剂,所述低分子醇促进剂优选甲醇、乙醇、丙醇、丁醇和乙二醇中的一种或多种,所述低分子醇促进剂的加入量优选为所述聚异丁烯质量的0.5%~3%。
根据本发明的聚异丁烯硫膦酸钙的优选制备方法,在聚异丁烯硫膦酸与氢氧化钙反应之后,可以通过过滤、水洗、重结晶等常规提纯方法中的一种或多种对产物进行提纯,并没有特别的限定。
根据本发明,所述聚异丁烯马来酸酐中聚异丁烯的数均分子量优选为300~10000,更优选400~5000,进一步优选500~3000。
根据本发明,在所述复合分散剂中,所述聚异丁烯硫膦酸钙与聚异丁烯马来酸酐的质量比优选为0.1~1:1~0.1。
根据本发明,所述二烷基二硫代磷酸锌中的烷基优选各自独立地选自C3~C10直链或支链烷基和C6~C10芳基。所述二烷基二硫代磷酸锌可以选用二丙基二硫代磷酸锌、二丁基二硫代磷酸锌、二辛基二硫代磷酸锌、二丁辛基二硫代磷酸锌和二苯基二硫代磷酸锌中的一种或多种,更优选选用二丁基二硫代磷酸锌、二辛基二硫代磷酸锌和二丁辛基二硫代磷酸锌中的一种或多种。根据本发明,所述二烷基二硫代氨基甲酸锌优选选自二乙基二硫代氨基甲酸锌、二丙基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸锌和二戊基二硫代氨基甲酸锌中的一种或多种,更优选选自二乙基二硫代氨基甲酸锌和/或二丁基二硫代氨基甲酸锌。
根据本发明,所述润滑基础油可以选用API I类油、API II类油、APIⅢ类油、APIIV类油和API V类油中的一种或多种,优选API I类油、API II类油和APIⅢ类油中的一种或多种。所述的I类油是馏分油经过白土精制、溶剂精制得到的润滑基础油,其黏度指数在80~100之间,其100℃运动黏度在1~40mm2/s之间;所述的II类油是馏分油经过加氢处理得到,其黏度指数在100~120之间,其100℃运动黏度在1~40mm2/s之间;所述的III类油是馏分油经过加氢异构得到,其黏度指数在120以上,其100℃运动黏度在1~40mm2/s之间。
根据本发明,所述润滑基础油更优选API I类油、API II类油和APIⅢ类油的混合物,其中API I类油占10%~50%,API II类油占10%~50%,APIⅢ类油占10%~50%,进一步优选API I类油和API II类油的混合物,其中API I类油占10%~90%、API II类油占10%~90%。
根据本发明,优选地,所述复合清净剂占润滑油组合物总质量的0.1%~30%(更优选0.2%~25%,进一步优选0.3%~15%);所述复合分散剂占润滑油组合物总质量的0.1%~15%(更优选0.2%~10%,进一步优选0.3%~8%);所述二烷基二硫代磷酸锌和/或二烷基二硫代氨基甲酸锌占润滑油组合物总质量的0.1%~8%(更优选0.2%~6%,进一步优选0.3%~3%);所述润滑基础油构成润滑油组合物的主要成分。
根据本发明,所述润滑油组合物的制备方法包括将其中的各种添加剂和润滑基础油混合的步骤。所述混合的温度优选为40~80℃,混合的时间优选为0.5~3h。
本发明的润滑油组合物具有优良的储存稳定性,在长期储存时不会出现外观浑浊现象,主要原因是聚异丁烯硫膦酸、聚异丁烯马来酸酐与超高碱值磺酸钙复合后,能够形成更加稳定的胶体体系。另外,本发明润滑油组合物中的超高碱值磺酸钙和复合分散剂复配后由于改善了储存稳定性,使得各种添加剂能够在配方中发挥相应的功能,因而本发明的润滑油组合物还具有优异的高温清净性、氧化安定性、酸中和性、抗磨减摩性,适用于船用柴油发动机的润滑,特别适用于二冲程低速十字头船用柴油机的润滑。
具体实施方式
除非特别说明,本发明中提到的百分比均为质量百分比。
合成不同数均分子量的聚异丁烯硫膦酸钙A、B、C,详述如下。
数均分子量680的聚异丁烯硫膦酸钙A的合成
在安装有电动搅拌的三口烧瓶中加入数均分子量为680的聚异丁烯1000g,加入P2S5 205g,从室温逐渐升温到200℃,升温速度为30℃/h,在200℃恒温反应10h,此时物料从无色逐渐变为棕色,通入12g水蒸汽进行反应,反应时间1.5h,然后加入1000g150SN,加入75g氢氧化钙、15g乙醇,在100℃反应2.5h,反应后过滤除渣,得到聚异丁烯硫膦酸钙产品A2262g,其中硫的质量分数为6.1%,磷的质量分数为2.0%,钙的质量分数为1.6%,碱值为43mgKOH/g。
数均分子量1000的聚异丁烯硫膦酸钙B的合成
在安装有电动搅拌的三口烧瓶中加入数均分子量为1000的聚异丁烯1000g,加入P2S5 140g,从室温逐渐升温到210℃,升温速度为30℃/h,在210℃恒温反应12h,此时物料从无色逐渐变为棕色,通入8.5g水蒸汽进行反应,反应时间2.5h,然后加入1000g 6号加氢油,加入65g氢氧化钙、10g丁醇,在100℃反应1.5h,反应后过滤除渣,得到聚异丁烯硫膦酸钙产品B 2158g,其中硫的质量分数为4.2%,磷的质量分数为1.5%,钙的质量分数为1.5%,碱值为40mgKOH/g。
数均分子量2300的聚异丁烯硫膦酸钙C的合成
在安装有电动搅拌的三口烧瓶中加入数均分子量2300的聚异丁烯1000g,加入P2S5120g,从室温逐渐升温到225℃,升温速度为30℃/h,在225℃恒温15h,此时物料从无色逐渐变为棕色,通入10.2g水蒸汽进行反应,反应时间4h,然后加入1000g150SN,加入50g氢氧化钙、8g乙二醇,在100℃反应3h,反应后过滤除渣,得到聚异丁烯硫膦酸钙产品C 2133g,其中硫的质量分数为3.6%,磷的质量分数为1.4%,钙的质量分数为1.1%,碱值为30.8mgKOH/g。
本发明的主要试验方法及试验原材料
1.所采用的试验方法
主要试验方法包括GB/T265、GB/T2541、GB/T3535、GB/T3142、SH/T0251。
高温清净性测定法
评定高温清净性的方法是成漆和成焦板试验,试验仪器为L-1型板式成焦器。成焦试验条件为:板温/油温=320℃/100℃,时间2h,停/开时间=45s/15s,成漆试验条件为:板温/油温=300℃/150℃,时间2h,连续进行。
抗氧化性测定法
评定抗氧化安定性的方法是PDSC试验,该试验是在TA 5000 DSC 2910热分析仪上进行,试验条件:升温速度为100℃/min,恒温60min,3.5MPa。
酸中和性测定
模拟船用气缸油在使用过程中油中碱性组分(主要是碳酸钙)与含硫燃料在燃烧过程中生成的硫酸所发生的中和反应。试验中取10g试油,水浴温度60℃,加入20%的硫酸溶液0.2mL进行中和反应。反应状态用生成的二氧化碳气体压力变化来表示,二氧化碳压力达到最大时说明中和反应结束。以中和反应结束所需时间表示酸中和速度的大小。时间越短,说明酸中和能力越强。
扩散性试验
模拟气缸油在气缸表面的扩散情况。用20mL试验油,在120℃恒温时,将试油滴加到光亮的铁板上,测量油滴扩散的直径。扩散直径越大,表明油品扩散性越好。
凝胶试验试验
用于评定气缸油被水污染后生成沉淀及凝胶的趋势。将1mL蒸馏水加入99mL试油中,搅拌15min,混合均匀后放置96h,测量产生的沉淀量、凝胶生成量。沉淀量、凝胶量越少,说明油品的抗凝胶性越好。
分散性试验
将1g样品、9g油泥和10g基础油一起放入烧杯中,150℃恒温加热搅拌,趁热取一滴试验油滴于滤纸上,放入烘箱恒温80℃保持1h,测量扩散圈与油圈的比值,比值越大,表明油泥分散性越好。
2.试验所用的主要润滑基础油,见表1。
表1试验用的润滑基础油
3.试验所用主要添加剂,见表2。
表2试验用的主要添加剂
4.试验所用主要气缸油复合剂,见表3。
表3试验用的船用气缸油复合剂
按照API50黏度级别调制70TBN船用气缸油,其中采用TBN600超高碱值磺酸钙、中低碱值清净剂、聚异丁烯硫膦酸钙、聚异丁烯马来酸酐、二烷基二硫代硫酸锌、二烷基二硫代氨基甲酸锌,润滑基础油采用API I类油、API II类油,调制得到实施例1~4。采用TBN600超高碱值磺酸钙、中低碱值清净剂、二烷基二硫代硫酸锌、T151、T152无灰分散剂、其它添加剂、润滑基础油,调制得到对比例1~4。采用市售的TBN70船用气缸油复合剂和润滑基础油调制得到对比例5、6。所述润滑基础油中含有15%的500SN、50%的150BS、35%的600N。各实施例和对比例的配方组成见表4,其性能评定结果见表5。
按照API50黏度级别调制40TBN船用气缸油,其中采用TBN600超高碱值磺酸钙、中低碱值清净剂、聚异丁烯硫膦酸钙、聚异丁烯马来酸酐、二烷基二硫代硫酸锌、二烷基二硫代氨基甲酸锌,润滑基础油采用API I类油、API II类油,调制得到实施例5~8。采用TBN600超高碱值磺酸钙、中低碱值清净剂、二烷基二硫代硫酸锌、T151、T152无灰分散剂、其它添加剂、润滑基础油,调制得到对比例7~10。采用市售的TBN40船用气缸油复合剂和润滑基础油调制得到对比例11、12。所述润滑基础油中含有10%的500SN、50%的150BS、40%的600N。各实施例和对比例的配方组成见表6,其性能评定结果见表7。
表4 70TBN船用气缸油的实施例及对比例
表5 70TBN船用气缸油的性能测试
通过表4、表5可以看出,实施例1~4所调制的5070船用气缸油具有透明的外观、优良的储存稳定性、清净性能、抗磨性能、扩散性能、酸中和性能、抗氧化性能。
表6 40TBN船用气缸油的实施例及对比例
表7 40TBN气缸油的性能测试
通过表6、表7可以看出,实施例5~8所调制的5040船用气缸油具有透明的外观、优良的储存稳定性、清净性能、抗磨性能、扩散性能、酸中和性能、抗氧化性能。
Claims (11)
1.润滑油组合物,包括复合清净剂、复合分散剂、二烷基二硫代磷酸锌和/或二烷基二硫代氨基甲酸锌、润滑基础油;其中所述复合清净剂为超高碱值清净剂和中低碱值清净剂的混合物,所述复合分散剂为聚异丁烯硫膦酸钙和聚异丁烯马来酸酐的混合物。
2.按照权利要求1所述的润滑油组合物,其特征在于,所述的超高碱值清净剂选自碱值大于590mgKOH/g的磺酸钙;所述的中低碱值清净剂选自碱值为20~150mgKOH/g的烷基苯磺酸钙、磺酸锂、烷基水杨酸钙和硫化烷基酚钙中的一种或多种。
3.按照权利要求1所述的润滑油组合物,其特征在于,在所述复合清净剂中,所述超高碱值清净剂与中低碱值清净剂的质量比为1:0.1~0.5。
4.按照权利要求1所述的润滑油组合物,其特征在于,所述聚异丁烯硫膦酸钙中聚异丁烯的数均分子量为300~10000(优选400~5000,更优选500~3000);所述聚异丁烯马来酸酐中聚异丁烯的数均分子量为300~10000(优选400~5000,更优选500~3000)。
5.按照权利要求1所述的润滑油组合物,其特征在于,所述聚异丁烯硫膦酸钙的制备方法包括:使聚异丁烯与P2S5反应生成聚异丁烯硫膦酸酐,然后与水反应生成聚异丁烯硫膦酸,再与氢氧化钙反应,收集产物。
6.按照权利要求5所述的润滑油组合物,其特征在于,所述聚异丁烯的数均分子量为300~10000(优选400~5000,更优选500~3000);聚异丁烯与P2S5反应的温度为150~250℃,反应时间为1~15h;所述聚异丁烯硫膦酸酐与水反应的温度为100~250℃,反应时间为1~20h;所述聚异丁烯硫膦酸与氢氧化钙反应的温度为50~200℃,反应时间为1~8h;所述聚异丁烯、P2S5、水、氢氧化钙之间的摩尔比为1~5:1~3:1~3:1~3。
7.按照权利要求5所述的润滑油组合物,其特征在于,在所述聚异丁烯硫膦酸与氢氧化钙的反应中加入低分子醇促进剂(所述低分子醇促进剂优选甲醇、乙醇、丙醇、丁醇和乙二醇中的一种或多种,所述低分子醇促进剂的加入量优选为所述聚异丁烯质量的0.5%~3%)。
8.按照权利要求1所述的润滑油组合物,其特征在于,在所述复合分散剂中,所述聚异丁烯硫膦酸钙与聚异丁烯马来酸酐的质量比为0.1~1:1~0.1。
9.按照权利要求1所述的润滑油组合物,其特征在于,所述二烷基二硫代磷酸锌中的烷基各自独立地选自C3~C10直链或支链烷基和C6~C10芳基;所述二烷基二硫代氨基甲酸锌选自二乙基二硫代氨基甲酸锌、二丙基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸锌和二戊基二硫代氨基甲酸锌中的一种或多种;所述润滑基础油选自API I类油、API II类油、APIⅢ类油、API IV类油和APIV类油中的一种或多种。
10.按照权利要求1~9之一所述的润滑油组合物,其特征在于,所述复合清净剂占润滑油组合物总质量的0.1%~30%(优选0.2%~25%);所述复合分散剂占润滑油组合物总质量的0.1%~15%(优选0.2%~10%);所述二烷基二硫代磷酸锌和/或二烷基二硫代氨基甲酸锌占润滑油组合物总质量的0.1%~8%(优选0.2%~6%);所述润滑基础油构成润滑油组合物的主要成分。
11.权利要求1~10之一所述的润滑油组合物的制备方法,包括将其中的各种添加剂和润滑基础油混合的步骤。
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