WO2016086857A1 - 一种船用柱塞式发动机润滑油组合物 - Google Patents

一种船用柱塞式发动机润滑油组合物 Download PDF

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WO2016086857A1
WO2016086857A1 PCT/CN2015/096189 CN2015096189W WO2016086857A1 WO 2016086857 A1 WO2016086857 A1 WO 2016086857A1 CN 2015096189 W CN2015096189 W CN 2015096189W WO 2016086857 A1 WO2016086857 A1 WO 2016086857A1
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lubricating oil
oil composition
engine lubricating
alkyl
composition according
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PCT/CN2015/096189
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English (en)
French (fr)
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冯涛
于军
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中国石油天然气股份有限公司
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Publication of WO2016086857A1 publication Critical patent/WO2016086857A1/zh

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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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential

Definitions

  • the present invention relates to an engine lubricating oil composition, and more particularly to a marine ramjet lubricating oil composition.
  • the marine engine can be divided into two strokes and four strokes according to the stroke.
  • the four-stroke engine is often a ramjet engine
  • the lubricating oil is medium-speed engine oil.
  • new engines with higher burst pressure and longer stroke have put forward new requirements for lubrication.
  • the corresponding lubricants have also appeared with some new technologies, such as the emergence of salicylate detergents for solving engine piston carbon deposition technology, to a large extent for new engines. Lubrication provides a better solution.
  • Marine medium speed machines generally use heavy fuel, so they contain a certain amount of asphaltenes. If the asphaltene is not completely burned, it will form some black spots on the engine piston head and skirt, which will affect the normal operation of the engine. By using a salicylate detergent in the lubricating oil, the black spot problem can be effectively solved.
  • Alkyl sulfonate detergent has excellent rust resistance, high base value, low production cost and great economic advantage. However, it is generally not compatible with alkyl salicylates for the preparation of lubricating oils, which are easily combined with alkyl salicylate detergents to precipitate and affect the use.
  • CN101586052A discloses a tubular piston marine engine lubricating oil composition for a medium speed compression ignition marine engine comprising the following components: a plurality of lubricating oils containing 50% by mass or more of a Group II base oil. Viscosity oils using two hydrocarbyl-substituted hydroxybenzoic acid overbased metal salt cleaners.
  • CN101962591A discloses a plunger engine lubricating oil composition
  • a plunger engine lubricating oil composition comprising (a) a major amount of a base stock comprising at least 90% by weight of a saturated hydrocarbon; and (b) a minor amount of a viscosity index of less than 70 and an alicyclic hydrocarbon content It is at least about 25% by weight of the base oil.
  • CN102086420B discloses a lubricating oil composition for a medium-speed cylindrical diesel engine for a ship, which is composed of an alkyl salicylate and has a good effect of suppressing the formation of black sludge.
  • CN102311839A discloses a plunger engine lubricating oil composition
  • a plunger engine lubricating oil composition comprising: (a) a major amount of a base stock of less than 90% by weight of saturated hydrocarbon; and (b) a base stock selected from the group consisting of: (i) an ester base stock, wherein the ester base stock is present in an amount greater than 10% by weight and not More than about 45% by weight, based on the total weight of the lubricating oil composition; (ii) an alkylated aromatic base stock; (iii) a base stock having an aromatics content of at least about 50% by weight, wherein The base stock having an aromatics content of at least about 50% by weight is not an aromatic extract; and mixtures thereof.
  • the plunger engine lubricating oil composition comprises at least (a) a major amount of a base stock selected from the group consisting of at least one Group III base stock, at least one Group IV base stock, and mixtures thereof; (b) at least one detergent additive (c) at least one dispersant additive, wherein the concentration of the at least one dispersant additive in the ramjet lubricating oil composition is based on the active substance based on the total weight of the lubricating oil composition At least about 0.1% by weight.
  • CN103160361A discloses a cylindrical piston engine lubricating oil composition
  • a cylindrical piston engine lubricating oil composition comprising: (a) a major amount of an oil of lubricating viscosity; (b) one or more carboxylate-containing detergents, the detergent comprising an alkane a salt of a substituted hydroxyaromatic carboxylic acid wherein at least about 50% of the alkyl portion of the alkyl substituted hydroxyaromatic carboxylic acid comprises a C26+ alkane derived from one or more normal alpha olefins (c) one or more zinc dithiophosphates in an amount of from about 0.02 to about 0.12 wt.%, based on the phosphorus content.
  • an object of the present invention is to provide a marine piston engine lubricating oil composition which is excellent in rust and oxidation resistance and low in cost.
  • the present invention provides a marine ramjet engine lubricating oil composition
  • a marine ramjet engine lubricating oil composition comprising, by mass percentage, the following components: an alkyl sulfonate detergent 1-15%, an alkyl salicylate Acid detergent 1-15%, synthetic polyether 0.1-5%, dispersant 0.1-5%, anti-wear agent 0.1-5%, class II base oil balance.
  • the alkyl sulfonate detergent to be used is a calcium sulfonate having a carbon chain length of C12-C24 and a base number of 380 to 420 mgKOH/g.
  • the calcium alkylsulfonate used is calcium petroleum sulfonate or synthetic calcium sulfonate.
  • the alkyl portion of the alkyl salicylate detergent employed comprises an alkyl group derived from one or more normal alpha olefin structures, the carbon chain of the alkyl group The length is C26-C30.
  • an alkane derived from one or more normal ⁇ -olefin structures is employed.
  • the chain length of the base is 10-30% of the entire alkyl chain length of the alkyl salicylate detergent.
  • the synthetic polyether used is polymerized from at least two of ethylene oxide, propylene oxide and butylene oxide, and the synthetic polyether has a viscosity average molecular weight of 1,000. -3000.
  • the dispersing agent to be used is at least one selected from the group consisting of monosuccinimide, bis-succinimide, and polysuccinimide.
  • the anti-wear agent used is a primary alcohol having a carbon chain length of C12-C18 or a secondary alcohol-based zinc thiophosphate having a carbon chain length of C12-C18.
  • the composition has a total base number of at least 12 mgKOH/g.
  • the composition has a total base number of 15 to 16 mgKOH/g.
  • the marine piston engine lubricating oil composition provided by the invention adopts a detergent composed of an alkyl sulfonate and an alkyl salicylate, which can maintain good anti-rust performance and has strong anti-oxidation. Performance; among them, the alkyl salicylate detergent has a special structure and can be well compatible with the insufficiently burned portion of the heavy fuel, thereby effectively suppressing the black sludge caused by the insufficiently burned portion of the heavy fuel.
  • the marine piston engine lubricating oil composition provided by the present invention can be applied to the type II base oil, so that it has better lubricating performance, and meets the marine piston engine and the new marine engine. Requirements for lubrication.
  • Examples 1-4 provide a marine ramjet engine lubricating oil composition, the composition and content of each of which is shown in Table 1.
  • Coke plate experiment Specification of experimental instrument: Coke plate tester (FTM 791-3462) produced by Koehler; oil temperature: 310 ° C; plate temperature: 110 ° C; turn-stop ratio: 20 /40; Experimental time: 3h; refueling amount: 300mL.
  • Coke plate tester FTM 791-3462
  • oil temperature 310 ° C
  • plate temperature 110 ° C
  • turn-stop ratio 20 /40
  • Experimental time 3h
  • refueling amount 300mL.
  • the petroleum sulfonate detergent has a carbon chain length of C14-C28 and a base value of 340 mgKOH/g; the synthetic calcium sulfonate has a carbon chain length of C16-C24 and a base number of 330 mgKOH/g; salicylic acid
  • the salt detergent refers to a kind of detergent with o-hydroxy-benzoic acid substituted with para-alkyl group as the main raw material, the carbon chain length is C26-C30, the base value is 290 mgKOH/g, and the polysuccinimide dispersant is composed of
  • the monobutylimide is polymerized and has a molecular weight of 1200; the synthetic polyether is polymerized from propylene oxide and butylene oxide, and its molecular weight is 2100; the zinc dialkyl thiophosphate has a carbon chain length of C16- Z18 primary alcohol thiophosphate.
  • Example 1 Example 2
  • Example 3 Example 4 Comparative example Base number (mg KOH/g) 45.4 52.3 47.8 48.4 50
  • the alkali value determination method in Table 2 is SH/T 02511993; the coke formation plate and the oxidation induction time are both self-built methods, and the conditions are as described in Examples 1-4.
  • the results of Table 2 show that the lubricating oil composition provided by the present invention has superior coke plate performance as compared with the lubricating oil composition of the comparative example, that is, it has superior detergency performance; and from the oxidation induction time condition, The lubricating oil composition provided by the present invention also has better oxidation resistance than the comparative examples.
  • the “Comparative Example” is the DCB4050H marine medium speed engine oil produced by Kunlun Lubricant Company.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

本发明提供了一种船用柱塞式发动机润滑油组合物。以质量百分比计，该组合物包括以下组分：烷基磺酸盐清净剂1-15％、烷基水杨酸盐清净剂1-15％、合成聚醚0.1-5％、分散剂0.1-5％、抗磨剂0.1-5％、II类基础油余量。本发明提供的船用柱塞式发动机润滑油组合物既具有较好的防锈、抗氧化性能，其中的烷基水杨酸盐清净剂，具有特殊的结构，能够与重质燃料中未充分燃烧部分很好地相溶，从而有效抑制重质燃料中未充分燃烧部分引起的黑色油泥。此外，由于加入了合成聚醚，本发明提供的船用柱塞式发动机润滑油组合物可以应用在II类基础油中，使其具有较好的润滑性能，满足各类船用柱塞式发动机对润滑的要求。

Description

一种船用柱塞式发动机润滑油组合物 技术领域
本发明涉及一种发动机润滑油组合物，尤其涉及一种船用柱塞式发动机润滑油组合物。
背景技术
船用发动机按冲程可分为二冲程和四冲程两种。其中四冲程发动机常为柱塞式发动机，使用润滑油为中速机油。随着发动机技术的发展，新式更高爆发压力、更长冲程等发动机均对润滑提出了新的要求。而近年来伴随着发动机技术的发展，相应的润滑油也出现了一些新技术与之匹配，如解决发动机活塞积炭技术的水杨酸盐清净剂的出现，在很大程度上为新式发动机的润滑提供了较好的解决方案。
船用中速机一般使用重质燃料，因此其含有一定量的沥青质。沥青质如果不完全燃烧，便会在发动机活塞头及裙部形成一些黑斑，从而影响到发动机的正常运行。而通过在润滑油中使用水杨酸盐清净剂，能够有效解决这种黑斑问题。
烷基磺酸盐清净剂具备较优异的防锈性能，且具备较高碱值，生产成本低，有非常大的经济优势。但其与烷基水杨酸盐一般不能一起用于调制润滑油，其易于与烷基水杨酸盐清净剂结合析出沉淀而影响使用。
随着全球基础油炼制工艺的改进，越来越多的炼厂具备生产II类基础油的能力。而在国内，有报道称国内II类基础油产量已经达到全部基础油的30％，而这种份额将会随着旧工艺的淘汰和新炼厂的建立进一步增加。在价格上，II类基础油与I类基础油的差距已经越来越小，这对于润滑油生产也将起到一定促进作用，即将可能使用越来越多量的II类基础油来替代I类基础油。
CN101586052A公开了一种用于中速压燃式船用发动机的筒状活塞船用发动机润滑油组合物，包含以下组分：多数量的一种含有50质量％或更多第II类基本油料的具有润滑粘度的油，其使用的是两种烃基取代的羟基苯甲酸高碱性金属盐清洗剂。
CN101962591A公开了一种柱塞发动机润滑油组合物，其包含(a)主要量的包含至少90重量％饱和烃的基础油料；和(b)次要量的粘度指数小于70且脂环族烃含量为至少约25重量％的基础油。
CN102086420B公开了一种船用中速筒状柴油机用润滑油组合物，由烷基水杨酸盐构成，具备较好的抑制黑色油泥生成的作用。
CN102311839A公开了一种柱塞发动机润滑油组合物，其包含：(a)主要量的含有至 少90重量％饱和烃的基础油料；和(b)选自由以下物质组成的组中的基础油料：(i)酯类基础油料，其中所述酯类基础油料的存在量大于10重量％且不大于约45重量％，基于所述润滑油组合物的总重量计；(ii)烷基化的芳族基础油料；(iii)具有至少约50重量％的芳族化合物含量的基础油料，其中所述具有至少约50重量％芳族化合物含量的基础油料不是芳族化合物萃取物；和它们的混合物。
CN102549129A公开了一种柱塞发动机润滑油组合物。该柱塞发动机润滑油组合物包括至少(a)主要量的选自至少一种III类基础油料、至少一种IV类基础油料及其混合物中的基础油料；(b)至少一种清净剂添加剂；(c)至少一种分散剂添加剂，其中基于所述润滑油组合物的总重量，所述至少一种分散剂添加剂在所述柱塞式发动机润滑油组合物中的浓度按活性物质计为至少约0.1wt％。
CN103160361A公开的是一种筒形活塞式发动机润滑油组合物，其包含：(a)主要量的润滑粘度油；(b)一种或多种含羧酸盐的清净剂，该清净剂包含烷基取代的羟基芳族羧酸的盐，其中所述烷基取代的羟基芳族羧酸的烷基部分的至少约50％包含衍生自一种或多种正构α-烯烃的C26+烷基；(c)以磷含量计约0.02-约0.12wt.％的量的一种或多种二硫代磷酸锌。
因此，研发一种具有良好性能的船用柱塞式发动机润滑油是本领域亟待解决的问题之一。
发明内容
为解决上述技术问题，本发明的目的在于提供一种防锈和抗氧化性能优异、造价低的船用柱塞式发动机润滑油组合物。
为达到上述目的，本发明提供了一种船用柱塞式发动机润滑油组合物，以质量百分比计，该组合物包括以下组分：烷基磺酸盐清净剂1-15％、烷基水杨酸盐清净剂1-15％、合成聚醚0.1-5％、分散剂0.1-5％、抗磨剂0.1-5％、II类基础油余量。
在上述润滑油组合物中，优选地，所采用的烷基磺酸盐清净剂为碳链长度为C12-C24的烷基磺酸钙，其碱值为380-420mgKOH/g。
在上述润滑油组合物中，优选地，所采用的烷基磺酸钙为石油磺酸钙或合成磺酸钙等。
在上述润滑油组合物中，优选地，所采用的烷基水杨酸盐清净剂的烷基部分包含衍生自一种或多种正构α-烯烃结构的烷基，该烷基的碳链长度为C26-C30。
在上述润滑油组合物中，优选地，所采用的衍生自一种或多种正构α-烯烃结构的烷 基的链长占烷基水杨酸盐清净剂的整个烷基链长的10-30％。
在上述润滑油组合物中，优选地，所采用的合成聚醚由环氧乙烷、环氧丙烷、环氧丁烷中的至少两种聚合而成，该合成聚醚的粘均分子量为1000-3000。
在上述润滑油组合物中，优选地，所采用的分散剂选自单丁二酰亚胺、双丁二酰亚胺、多丁二酰亚胺中的至少一种。
在上述润滑油组合物中，优选地，所采用的抗磨剂为碳链长度为C12-C18的伯醇或碳链长度为C12-C18的仲醇基硫代磷酸锌。
在上述润滑油组合物中，优选地，该组合物的总碱值至少为12mgKOH/g。
在上述润滑油组合物中，优选地，该组合物的总碱值为15-16mgKOH/g。
本发明提供的船用柱塞式发动机润滑油组合物采用烷基磺酸盐与烷基水杨酸盐复合构成的清净剂，既能保持较好的防锈性能，又能具有较强的抗氧化性能；其中的烷基水杨酸盐清净剂由于具有特殊的结构，能够与重质燃料中未充分燃烧部分很好地相溶，从而有效抑制重质燃料中未充分燃烧部分引起的黑色油泥。此外，由于加入了合成聚醚，本发明提供的船用柱塞式发动机润滑油组合物可以应用在II类基础油中，使其具有较好的润滑性能，满足船用柱塞式发动机以及新式船用发动机对润滑的要求。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
实施例1-4
实施例1-4提供了一种船用柱塞式发动机润滑油组合物，每个实施例中润滑油组合物的组分及含量如表1所示。
对实施例1-4和对比例分别进行成焦板实验和PDSC恒温法测定氧化诱导期实验，具体测试条件如下：
1)成焦板实验：实验仪器的规格型号：由Koehler(科勒)公司生产的成焦板试验仪(FTM 791-3462)；油温：310℃；板温：110℃；转停比：20/40；实验时间：3h；加油量：300mL。
2)PDSC恒温法测定氧化诱导期实验：实验仪器的规格型号：由美国TA仪器公司生产的差示扫描量热仪(Q20P)；温度：190℃；氧气压力：2.5MPa；氧气流速：无流速(静态)；样品皿的材质及直径：4mm×5mm；样品用量：3±0.2mg。
实验结果见表2。
表1 船用柱塞式发动机润滑油组合物的组分及含量(单位为％)
Figure PCTCN2015096189-appb-000001
上述表1中，石油磺酸钙清净剂的碳链长度为C14-C28，碱值为340mgKOH/g；合成磺酸钙的碳链长度为C16-C24，碱值为330mgKOH/g；水杨酸盐清净剂指以对位烷基取代的邻羟基-苯甲酸为主要原料的一类清净剂，其碳链长度为C26-C30，碱值为290mgKOH/g；聚丁二酰亚胺分散剂由单丁二酰亚胺聚合而成，其分子量为1200；合成聚醚由环氧丙烷与环氧丁烷聚合而成，其分子量为2100；二烷基硫代磷酸锌为碳链长度为C16-C18的伯醇基硫代磷酸锌。
表2 测试结果
性能 实施例1 实施例2 实施例3 实施例4 对比例
碱值(mg KOH/g) 45.4 52.3 47.8 48.4 50
成焦板焦重(mg) 42 53 38 40 108
氧化诱导时间(min) 85 78 95 88 32
表2中的碱值测定方法为SH/T 02511993；成焦板与氧化诱导时间均为自建方法，条件见实施例1-4所述的条件。
表2的结果表明，本发明提供的润滑油组合物与对比例的润滑油组合物相比具备较优异的成焦板性能，即其具备较优的清净性能；而从氧化诱导时间条件看，与对比例相比，本发明提供的润滑油组合物也具备较好的抗氧化性能。其中“对比例”为昆仑润滑油公司生产的DCB4050H船用中速机油。

Claims (10)

  1. 一种船用柱塞式发动机润滑油组合物，以质量百分比计，该组合物包括以下组分：烷基磺酸盐清净剂1-15％、烷基水杨酸盐清净剂1-15％、合成聚醚0.1-5％、分散剂0.1-5％、抗磨剂0.1-5％、II类基础油余量。
  2. 根据权利要求1所述的柱塞式发动机润滑油组合物，其中：所述烷基磺酸盐清净剂为碳链长度为C12-C24的烷基磺酸钙，其碱值为380-420mgKOH/g。
  3. 根据权利要求2所述的柱塞式发动机润滑油组合物，其中：所述烷基磺酸钙为石油磺酸钙或合成磺酸钙。
  4. 根据权利要求1至3中任一项所述的柱塞式发动机润滑油组合物，其中：所述烷基水杨酸盐清净剂的烷基部分包含衍生自一种或多种正构α-烯烃结构的烷基，该烷基的碳链长度为C26-C30。
  5. 根据权利要求4所述的柱塞式发动机润滑油组合物，其中：所述衍生自一种或多种正构α-烯烃结构的烷基的链长占烷基水杨酸盐清净剂的整个烷基链长的10-30％。
  6. 根据权利要求1所述的柱塞式发动机润滑油组合物，其中：所述合成聚醚由环氧乙烷、环氧丙烷、环氧丁烷中的至少两种聚合而成，该合成聚醚的粘均分子量为1000-3000。
  7. 根据权利要求1所述的柱塞式发动机润滑油组合物，其中：所述分散剂选自单丁二酰亚胺、双丁二酰亚胺、多丁二酰亚胺中的至少一种。
  8. 根据权利要求1所述的柱塞式发动机润滑油组合物，其中：所述抗磨剂为碳链长度为C12-C18的伯醇或仲醇基硫代磷酸锌。
  9. 根据权利要求1所述的柱塞式发动机润滑油组合物，其中：该组合物的总碱值至少为12mgKOH/g。
  10. 根据权利要求9所述的柱塞式发动机润滑油组合物，其中：该组合物的总碱值为15-16mgKOH/g。
PCT/CN2015/096189 2014-12-05 2015-12-02 一种船用柱塞式发动机润滑油组合物 WO2016086857A1 (zh)

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